Surface-Treating Agents, Surface-Treated Powders, And Cosmetics Comprising The Same

ABSTRACT

To provide surface-treating agents that can provide excellent hydrophobicity to powder and can improve its rinsability, to provide surface-treated powders that are treated with the surface-treating agent, and to provide cosmetics that comprise the surface-treated powder. A surface-treating agent consisting of a polymer which comprises a monomer (A) represented by the general formula (1) described below as a constituent monomer. 
     
       
         
         
             
             
         
       
     
     (wherein R 1  represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2  represents an alkylene group having 4 to 22 carbon atoms, X 1  represents an —NH— group or an oxygen atom, and M 1  represents a hydrogen atom or a monovalent inorganic or organic cation.)

RELATED APPLICATIONS

This application claims the priority of Japanese Patent Application No.2004-294618 filed on Oct. 7, 2004 and Japanese Patent Application No.2004-294619 filed on Oct. 7, 2004, which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to surface-treating agents,surface-treated powders, and cosmetics comprising the same, and inparticular, relates to the improvement of hydrophobicity and rinsabilityof the powder used in cosmetics.

2. Prior Art

For cosmetics, especially for makeup cosmetics, the beautifying effect,which makes people beautiful, is naturally expected. In addition, thesustainability of the beautifying effect, namely, long-lasting makeup isone of very important required characteristics. Thus, in the developmentof cosmetic base material, one of important themes has beenlonger-lasting makeup. In the field of makeup cosmetics, oily bases areoften used so that the makeup does not deteriorate with moisture such assweat, tears, and saliva. When hydrophilic powder is blended in an oilybase, the powder easily separates from the base. In addition, thehydrophilic powder is washed away with moisture, and it becomes a majorcause of makeup deterioration. In the past, when powder was blended intocosmetics, the powder that had been hydrophobized in advance was oftenused for blending.

There are numerous methods for the hydrophobization of powder used incosmetics. For example, a powder hydrophobization method, in whichhigher fatty acids, higher alcohols, hydrocarbons, triglycerides,esters, silicones such as silicone oil and silicone resin, or fluorinecompounds are used, has been practiced to cover the surface ofhydrophilic powder. In particular, the powder hydrophobizing treatment,in which silicones are used as the surface-treating agent, can provideexcellent hydrophobicity. Thus, numerous methods have been establishedso far (refer to patent literatures 1 and 2, for example). In recentyears, a method in which a copolymer of acrylic acid and acrylic acidester is used as the powder surface-treating agent is also known (referto patent literature 3, for example).

On the other hand, the rinsability of cosmetics is also one of theimportant required characteristics. When the above-describedconventional hydrophobized powder is blended, a longer-lasting makeupcan be achieved. However, the makeup cannot be easily rinsed away withwater, even when soap is used, because of the excellent hydrophobicity.Therefore, oily cleansing agents have been widely used, however, it alsobecomes necessary to wash away this oily cleansing agent with soap.Thus, the burden to users becomes high. When hydrophilic powder isblended to allow easy rinsing, the makeup easily deteriorates and themakeup is short-lasting as described above. Thus, it has been a verydifficult theme to satisfy both the characteristics: long lasting makeupin use and easy rinsing after use.

Patent literature 1: Japanese Unexamined Patent Publication S60-163973Patent literature 2: Japanese Unexamined Patent Publication S62-177070Patent literature 3: Japanese Unexamined Patent Publication H8-337514SUMMARY OF THE INVENTION

The present invention was made in view of the above-described problem,and the objects of the invention are to provide surface-treating agentsthat can provide excellent hydrophobicity to powder and can improve itsrinsability, to provide surface-treated powders that are generated withthe surface-treating agent, and to provide cosmetics that comprise thesurface-treated powder.

The present inventors have diligently researched in view of theabove-described problem and focused on the pH-responsivehydrophobicity-hydrophilicity change. The present inventors treated thesurface of the powder with a polymer that comprised, as a constituentmonomer, an acrylic derivative of a specific structure and found thatthe hydrophobicity-hydrophilicity of the surface-treated powderdramatically changes with the pH change. That is, the surface-treatedpowder with the above-described polymer shows excellent hydrophobicityin the acidic to neutral region, where general cosmetics are used. Onthe other hand, the surface of the powder becomes hydrophilic in themoderately basic conditions that are generated with soap water. As aresult, we found that when the surface-treated powder was blended incosmetics, the makeup was long-lasting; nevertheless, the makeup couldbe easily rinsed away with water by using soap, thus leading to thecompletion of the present invention.

The present inventors have diligently researched in view of theabove-described problem, and focused on the pH-responsivehydrophobicity-hydrophilicity change. The present inventors used apolymer that comprised, as a constituent monomer, an acrylic derivativeof a specific structure as the surface-treating agent of the powder andfound that the hydrophobicity-hydrophilicity of the surface-treatedpowder dramatically changes with the pH change. That is, the powdertreated with the above-described surface-treating agent shows excellenthydrophobicity in the acidic to neutral region, where general cosmeticsare used. On the other hand, the surface of the powder becomeshydrophilic in the moderately basic conditions that are generated withsoap water. As a result, when the treated powder is blended incosmetics, the makeup is long-lasting; nevertheless, the makeup can beeasily rinsed away with water by using soap. Thus, the present inventorsfound that the excellent hydrophobicity could be provided to the powderby treating the powder surface with the above-described surface-treatingagent and that the rinsability could significantly be improved, thusleading to the completion of the present invention.

The first subject of the present invention is a surface-treating agent,which consists of a polymer comprising a monomer (A) represented by thegeneral formula (1) described below as a constituent monomer.

(wherein R¹ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R² represents an alkylene group having 4 to 22 carbonatoms, X¹ represents an —NH— group or an oxygen atom, and M¹ representsa hydrogen atom or a monovalent inorganic or organic cation.)

In addition, it is preferable that the polymer of the surface-treatingagent comprises the above-described monomer (A) equal to or more than 70mole % of the total constituent monomers.

In addition, it is preferable that the polymer of the above-describedsurface-treating agent, further comprises a monomer (B), which isrepresented by any of the below-described general formulas (2) to (7) asa constituent monomer.

(wherein R³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁴ represents an alkylene group having 1 to 4 carbonatoms, X² represents an —NH— group or an oxygen atom, and M² representsa hydrogen atom or a monovalent inorganic or organic cation.)

(wherein R⁵ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁶ represents an alkyl group having 1 to 10 carbon atoms,a fluoroalkyl group, an aminoalkyl group, or a hydroxyalkyl group, andX³ represents an —NH— group or an oxygen atom.)

(wherein R⁷ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁸ represents an alkylene group having 1 to 4 carbonatoms, R⁹s may be the same or different and each represents a hydrogenatom or an alkyl group having 1 to 4 carbon atoms, X⁴ represents an —NH—group or an oxygen atom, and Y⁻ represents a monovalent organic orinorganic anion.)

(wherein R¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹¹ represents an alkylene group having 1 to 4 carbonatoms, R¹² represents a hydrogen atom or an alkyl group having 1 to 4carbon atoms, X⁵ represents an —NH— group or an oxygen atom, and lstands for an integer of 1 to 100.)

(wherein R¹³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹⁴s may be the same or different and each represents ahydrogen atom or an alkyl group having 1 to 4 carbon atoms, R¹⁵represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,X⁶ represents an —NH— group or an oxygen atom, and m stands for aninteger of 1 to 100.)

(wherein R¹⁶ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹⁷ represents an alkylene group having 1 to 4 carbonatoms, X⁷ represents an —NH— group or an oxygen atom, M³ represents ahydrogen atom or a monovalent inorganic or organic cation, and n standsfor an integer of 1 to 100.)

In addition, the mole ratio (A):(B) of the monomer (A) and the monomer(B) in the surface-treating agent is preferably within the range from70:30 to 99.9:0.1.

The second subject of the present invention is surface-treated powder,which is coated with the surface-treating agent on the powder surface.The amount of surface-treating agent coated on the powder, expressed inthe mass ratio of the polymer to the powder, is preferably within therange from 3:97 to 40:60.

The third subject of the present invention is cosmetics, which comprisesthe surface-treated powder.

EFFECT OF THE INVENTION

The excellent hydrophobicity can be provided to the powder, and therinsability can be significantly improved by treating the powder surfacewith the surface-treating agent of the present invention. Therefore,when the surface-treated powder treated with the surface-treating agentof the present invention is blended into cosmetics, the makeup can beeasily rinsed away with water by using soap although the makeup islong-lasting.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a picture of pH 5 buffer solutions containing thesurface-treated powder treated with various surface-treating agents (MAUhomopolymer or MAU/AMPS copolymers) of the present invention.

FIG. 2 shows a picture of pH 10 buffer solutions containing thesurface-treated powder treated with various surface-treating agents (MAUhomopolymer or MAU/AMPS copolymers) of the present invention.

FIG. 3 shows the results of NMR measurement of a surface-treating agent(MMPA homopolymer) of the present invention.

FIG. 4 shows a picture of pH 5 and pH 10 buffer solutions containing thesurface-treated powder treated with a surface-treating agent (MMPAhomopolymer) of the present invention.

FIG. 5 shows the results of infrared spectroscopic measurement of asurface-treating agent (MMPA homopolymer) of the present invention underthe untreated and treated (with 1 M NaOH solution) conditions.

DESCRIPTION OF THE PREFERRED EMBODIMENT

In the following, the preferable mode for carrying out the presentinvention is described in detail.

The surface-treating agent of the present invention consists of apolymer which comprises a monomer (A) represented by the above-describedgeneral formula (1) as a constituent monomer.

The monomer (A) represented by the general formula (1) is a compound inwhich a fatty acid is attached to acrylic acid, alkyl-substitutedacrylic acid, acrylamide, or alkyl-substituted acrylamide. In thegeneral formula (1), R¹ represents a hydrogen atom or an alkyl grouphaving 1 to 3 carbon atoms. When R¹ is an alkyl group, it can be eitherlinear or branched. R¹ is preferably a hydrogen atom or a methyl group.In the general formula (1), R² is an alkylene group having 4 to 22carbon atoms. The alkylene group can be either linear or branched.Examples of R² include an octylene group having 8 carbon atoms, anundecylene group having 11 carbon atoms, and a dodecylene group having12 atoms. In addition, R² may include an aromatic ring or carbon-carbondouble bonds in the structure, for example, R² may be a vinylene group,a methylphenylene group, or a vinylphenylene group. In the generalformula (1), X¹ is an —NH— group or an oxygen atom, and it is preferablyan —NH— group. In the general formula (1), M¹ is a hydrogen atom or amonovalent inorganic or organic cation. The monovalent inorganic ororganic cation can be any cation so far as it can form a carboxylatesalt. Examples of the monovalent inorganic cation include sodium ion,potassium ion, and lithium ion, and examples of the monovalent organiccation include ammonium ion, monoethanolammonium ion, andtriethanolammonium ion. In addition, M¹ can be reversibly converted,after the preparation of the polymer, to the form of the carboxylic acid(M¹=hydrogen) or sodium salt (M¹=sodium) with an appropriate amount ofdilute hydrochloric acid or dilute sodium hydroxide solution.

Examples of the monomer (A) of the present invention include11-methacrylamidoundecanoic acid, 8-acrylamidooctanoic acid,12-acrylamidododecanoic acid, 12-methacrylamidododecanoic acid, and3-{4-[(methacryloxy)methyl]phenyl}acrylic acid. A polymer of the presentinvention may include one or more kind of the above-described monomer(A) as the constituent monomer.

A polymer of the present invention preferably comprises theabove-described monomer (A) in equal to or more than 70 mole % of thetotal constituent monomers. If the content of the monomer (A) is lessthan 70 mole %, the effectiveness in the hydrophobicity-hydrophilicityadjustment is small, and desired characteristics may not be provided tothe powder. The content of the monomer (A) is preferably equal to ormore than 90 mole %. In the polymer of the present invention, theabove-described monomer (A) may account for the total amount of theconstituent monomer.

In the polymer of the present invention, a monomer (B) represented byany of the above-described general formulas (2) to (7) can be desirablyused as a constituent monomer in addition to the above-described monomer(A).

The monomer represented by the general formula (2) is a compound inwhich an alkyl sulfonic acid is attached to acrylic acid,alkyl-substituted acrylic acid, acrylamide, or alkyl-substitutedacrylamide. In the general formula (2), R³ is a hydrogen atom or analkyl group having 1 to 3 carbon atoms. When R³ is an alkyl group, itcan be either linear or branched. R³ is preferably a hydrogen atom or amethyl group. In the general formula (2), R⁴ is an alkylene group having1 to 4 carbon atoms. The alkylene group can be either linear orbranched. Examples of R⁴ include a methylene group, an ethylene group,and a propylene group, and it is preferably an ethylene group or apropylene group. In the general formula (2), X² is an —NH— group or anoxygen atom, and it is preferably an —NH— group. In the general formula(2), M² is a hydrogen atom or a monovalent inorganic or organic cation.The monovalent inorganic or organic cation can be any cation so far asit can form a sulfonic acid. Examples of the monovalent inorganic cationinclude sodium ion, potassium ion, and lithium ion, and examples of themonovalent organic cation include ammonium ion, monoethanolammonium ion,and triethanolammonium ion. In addition, M² can be reversibly converted,after the preparation of a polymer, to the form of the sulfonic acid(M²=hydrogen) or sodium salt (M²=sodium) with an appropriate amount ofdilute hydrochloric acid or dilute sodium hydroxide solution.

Examples of the monomer represented by the general formula (2) include2-acrylamido-2-methylpropanesulfonic acid and potassium3-methacryloxypropanesulfonate.

The monomer represented by the general formula (3) is a compound inwhich an alkyl group is attached to acrylic acid, alkyl-substitutedacrylic acid, acrylamide, or alkyl-substituted acrylamide. In thegeneral formula (3), R⁵ is a hydrogen atom or an alkyl group having 1 to3 carbon atoms. When R⁵ is an alkyl group, it can be either linear orbranched. R⁵ is preferably a hydrogen atom or a methyl group. In thegeneral formula (3), R⁶ is an alkyl group having 1 to 10 carbon atoms, afluoroalkyl group having equal to or more than one fluorine atom, anaminoalkyl group having equal to or more than one amino group, or ahydroxyalkyl group having equal to or more than one hydroxyl group.These alkyl groups can be either linear or branched. When R⁶ is an alkylgroup, the examples include a methyl group, an ethyl group, a pentylgroup, an octyl group, a decyl group, and a 2-ethylhexyl group, and itis preferably a 2-ethylhexyl group. When R⁶ is a fluoroalkyl group, theexamples include a trifluoromethyl group, a trifluoroethyl group, and atetrafluoropropyl group, and it is preferably a trifluoroethyl group ora tetrafluoropropyl group. When R⁶ is an aminoalkyl group, the examplesinclude an aminoethyl group and aminopropyl group, and anN,N-dimethylaminoethyl group, and it is preferably anN,N-dimethylaminoethyl group. When R⁶ is a hydroxyalkyl group, theexamples include a hydroxyethyl group, a hydroxypropyl group, and adihydroxypropyl group, and it is preferably a hydroxyethyl group. In thegeneral formula (3), X³ is an —NH— group or an oxygen atom.

Examples of the monomer represented by the general formula (3) include2-ethylhexyl acrylate, 2,2,2-trifluoropropyl acrylate,2,2,3,3-tetrafluoropropyl methacrylate, 2-(N,N-dimethylamino)ethylacrylate, 2-dimethylaminoethyl methacrylate, N-hydroxyethyl acrylate,and glycerol monomethacrylate.

The monomer represented by the general formula (4) is a compound inwhich an alkyl ammonium salt is attached to acrylic acid,alkyl-substituted acrylic acid, acrylamide, or alkyl-substitutedacrylamide. In the general formula (4), R⁷ is a hydrogen atom or analkyl group having 1 to 3 carbon atoms. When R⁷ is an alkyl group, itcan be either linear or branched. R⁷ is preferably a hydrogen atom or amethyl group. In the general formula (4), R⁸ is an alkylene group having1 to 4 carbon atoms. The alkylene group can be either linear orbranched. Examples of R⁸ include a methylene group, an ethylene group,and a propylene group, and it is preferably an ethylene group orpropylene group. R⁹s may be the same or different and each represents ahydrogen atom or an alkyl group having 1 to 4 carbon atoms. When R⁹ isan alkyl group, it can be either linear or branched. R⁹ is preferably ahydrogen atom or a methyl group. In the general formula (4), X⁴ is an—NH— group or an oxygen atom. Y⁻ is a monovalent organic or inorganicanion, and it can be any anion so far as it can form a quaternaryammonium salt. Examples of Y⁻ include monovalent inorganic anions suchas chloride ion, fluoride ion, and iodide ion; and monovalent organicanions such as sulfate ion, acetate ion, benzenesulfonate ion, andphosphate ion.

Examples of the monomer represented by the general formula (4) includeN,N-dimethylaminoethyl acrylate methyl chloride and N,N-dimethylaminoacrylamide methyl chloride.

The monomer represented by the general formula (5) is a compound, inwhich a (poly) alkylene oxide is attached to acrylic acid,alkyl-substituted acrylic acid, acrylamide, or alkyl-substitutedacrylamide. In the general formula (5), R¹⁰ is a hydrogen atom or analkyl group having 1 to 3 carbon atoms. When R¹⁰ is an alkyl group, itcan be either linear or branched. R¹⁰ is preferably a hydrogen atom or amethyl group. In the general formula (5), R¹¹ is an alkylene grouphaving 1 to 4 carbon atoms, and the alkylene group can be either linearor branched. Examples of R¹¹ include a methylene group, an ethylenegroup, and a propylene group, and it is preferably an ethylene group ora propylene group. R¹² is a hydrogen atom or an alkyl group having 1 to4 carbon atoms, and the examples include a hydrogen atom, a methylgroup, and an ethyl group. R¹² is preferably a methyl group. In thegeneral formula (5), X⁵ is an —NH— group or an oxygen atom. The letter lindicates the mole number of attached alkylene oxides, and it is aninteger of 1 to 100.

Examples of the monomer represented by the general formula (5) includemethoxypolyethylene glycol methacrylate.

The monomer represented by the general formula (6) is a compound inwhich polysiloxane is attached to acrylic acid, alkyl-substitutedacrylic acid, acrylamide, or alkyl-substituted acrylamide. In thegeneral formula (6), R¹³ is a hydrogen atom or an alkyl group having 1to 3 carbon atoms. When R¹³ is an alkyl group, it can be either linearor branched. R¹³ is preferably a hydrogen atom or a methyl group. In thegeneral formula (6), R¹⁴s may be the same or different and eachrepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.When R¹⁴ is an alkyl group, it can be either linear or branched. R¹⁴ ispreferably a hydrogen atom or a methyl group. R¹⁵ is a hydrogen atom oran alkyl group having 1 to 4 carbon atoms, and the examples include ahydrogen atom, a methyl group, and an ethyl group. R¹⁵ is preferably ahydrogen atom or a methyl group. In the general formula (6), X⁶ is an—NH— group or an oxygen atom. The letter m indicates the mole number ofattached siloxane groups, and it is an integer of 1 to 100.

Examples of the monomer represented by the general formula (6) includemethacryloxy-modified silicones.

The monomer represented by the general formula (7) is a compound inwhich alkylphosphoric acid (salt) is attached to acrylic acid,alkyl-substituted acrylic acid, acrylamide, or alkyl-substitutedacrylamide. In the general formula (7), R¹⁶ is a hydrogen atom or analkyl group having 1 to 3 carbon atoms. When R¹⁶ is an alkyl group, itcan be either linear or branched. R¹⁶ is preferably a hydrogen atom or amethyl group. In the general formula (7), R¹⁷ is an alkylene grouphaving 1 to 4 carbon atoms, and the alkylene group can be either linearor branched. Examples of R¹⁷ include a methylene group, an ethylenegroup, and a propylene group, and it is preferably an ethylene group ora propylene group. In the general formula (7), X⁷ is an —NH— group or anoxygen atom. The letter n indicates the mole number of attached alkyleneoxides, and it is an integer of 1 to 100. In the general formula (7), M³is a hydrogen atom or a monovalent inorganic or organic cation. Themonovalent inorganic or organic cation can be any cation so far as itcan form a phosphate. Examples of the monovalent inorganic cationinclude sodium ion, potassium ion, and lithium ion, and examples of themonovalent organic cation include ammonium ion, monoethanolammonium ion,and triethanolammonium ion. In addition, M³ can be reversibly converted,after the preparation of a polymer, to the form of the phosphoric acid(M³=hydrogen) or sodium salt (M³=sodium) with an appropriate amount ofdilute hydrochloric acid or dilute sodium hydroxide solution.

Examples of the monomer represented by the general formula (7) include2-methacryloxyethyl phosphoric acid.

The polymer of the present invention may include one or more kind of anymonomer (B) represented by the above-described general formulas (2) to(7) as the constituent monomer.

The polymer of the present invention preferably comprises theabove-described monomer (B) in 1 to 30 mole % of the total constituentmonomers. If the content of the monomer (B) is less than 1 mole %, theblending effect cannot be achieved. If the content of the monomer (B) ismore than 30 mole %, the relative content of monomer (A) becomes small.As a result, desired characteristics may not be provided to the powder.

The polymer of the present invention can comprise a monomer other thanthe above-described monomers (A) and (B) as the constituent monomer sofar as the effect of the present invention is not undermined. Thecontent equal to or less than 30 mole % of the total constituentmonomers is satisfactory, and the content can be, for example, about 1to about 20 mole %. Examples of the monomer include acrylamide,methacrylamide, N-vinylpyrrolidone, ε-caprolactam, vinylalcohol, maleicanhydride, diallyldimethylammonium chloride, and styrene.

The polymer of the present invention can be obtained by polymerizingvarious monomers, including the above-described monomers, by publiclyknown polymerization methods. For example, homogeneous solutionpolymerization, heterogeneous solution polymerization, emulsionpolymerization, inverse emulsion polymerization, bulk polymerization,suspension polymerization, and precipitation polymerization can be used.For example, in the case of homogeneous solution polymerization, thepolymer of the present invention can be obtained by dissolving variousmonomers in a solvent, adding a radical polymerization initiator under anitrogen atmosphere, and heating the solution with stirring. Inaddition, the polymer of the present invention can be obtained by thepost-modification in which functional groups are attached to polyacrylicacid or polyacrylamide.

As the solvent for the polymerization, any solvent can be used so far asvarious monomers can be dissolved or suspended and it is an organicsolvent containing no water. Examples include alcohol solvents, such asmethanol, ethanol, propyl alcohol, isopropyl alcohol, and butyl alcohol;hydrocarbon solvents, such as hexane, heptane, octane, isooctane,decane, and liquid paraffin; ether solvents, such as dimethyl ether,diethyl ether, and tetrahydrofuran; ketone solvents, such as acetone andmethyl ethyl ketone; ester solvents, such as methyl acetate, ethylacetate, and butyl acetate; chlorine solvents, such as methylenechloride, chloroform, and carbon tetrachloride; dimethylformamide;diethylformamide; dimethyl sulfoxide; and dioxane. More than one kind ofthese solvents can be mixed for use. It is usually preferable to selecta solvent that has a higher boiling point than the initiationtemperature of the polymerization initiator.

The polymerization initiator is not limited in particular so far as itcan initiate radical polymerization, and examples include peroxides suchas benzoyl peroxide, azo compounds such as azobisisobutyronitrile (AIBN)and dimethyl 2,2′-azobis(isobutyrate), and persulfate polymerizationinitiators such as potassium persulfate and ammonium persulfate. Thepolymerization can be conducted, without depending on a polymerizationinitiator, by a photochemical reaction, radiation, or the like. Thepolymerization temperature should be equal to or more than thepolymerization initiation temperature of each polymerization initiator.For example, about 50 to about 70° C. is usually suitable for theperoxide polymerization initiator.

The polymerization time is not limited in particular, and it is usuallyabout 30 minutes to about 24 hours. When a polymer with a relativelyhigh molecular weight is desirable, the desirable reaction time is about24 hours. If the reaction time is too short, the unreacted monomerremains and the molecular weight may turn out to be relatively small.The average molecular weight of the polymer of the present invention isnot limited in particular. If the degree of polymerization is more thanthat of oligomers, the desired effect can be achieved. However, theaverage molecular weight is preferably about 3000 to about 100 thousand.In polymerization by mixing more than one kind of monomer, a copolymerin which various monomers are randomly added can usually be obtained.

The surface-treated powder of the present invention is characterized inthat the above-obtained polymer is coated on the powder surface.

The polymer used in the present invention has carboxyl groups, which arederived from the above-described monomer (A), on the side chains of thepolymer. The carboxyl group changes to a hydrophobic carboxylic acid(—COOH) under acidic to neutral conditions and changes to a hydrophiliccarboxylate ion (—COO⁻M⁺) under basic conditions. Therefore, the powderthe surface of which is treated with this polymer, for example, isconsidered to be hydrophobic in the acidic to neutral environment andhydrophilic in the basic environment. As a result, the pH-responsivehydrophobicity-hydrophilicity change is exhibited.

When the thus obtained surface-treated powder is blended in cosmetics,the cosmetics show hydrophobicity in the acidic to neutral region, wherecosmetics are normally used, achieving long-lasting makeup.Nevertheless, when the surrounding becomes moderately basic with soap,the treated powder surface becomes hydrophilic and the makeup can beeasily rinsed away.

The above-described monomer (B) is not easily affected by pH, and themonomer shows a stable hydrophilic or hydrophobic property in the widerange of pH. Therefore, if a polymer is prepared by appropriatelyadjusting the ratio of the above-described monomer (A) and monomer (B)as the constituent monomers, the desirable hydrophobicity-hydrophilicitybalance, which is provided to the powder, can be achieved. For example,it is possible to increase the hydrophilicity by combining a monomer (B)represented by the general formula (2) with the above-described monomer(A). On the contrary, it is possible to increase the hydrophobicity bycombining a monomer (B) represented by the general formula (6) with theabove-described monomer (A). In addition, it is possible to increase theadsorption of powder to the polymer by utilizing an appropriate amountof the above-described monomer (B).

In the polymer used in the present invention, the mole ratio (A):(B) ofthe monomer (A) and the monomer (B) should preferably be adjusted withinthe range from 70:30 to 99.9:0.1. If the content of the monomer (A) isless than the ratio of 70:30, the treated powder will becomehydrophilic, and satisfactory hydrophobicity may not be achieved. On theother hand, if the content of the monomer (A) is more than the ratio of99.9:0.1, it will become difficult to adsorb a polymer on the powdersurface, and the stability of the powder may be negatively affected.

The powder used in the present invention is not limited in particular,and examples include inorganic powders, such as silicic acid, silicicanhydride, magnesium silicate, talc, kaolin, mica, bentonite, titanatedmica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide,titanium oxide, aluminum oxide, calcium sulfate, barium sulfate,magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide,ultramarine blue, iron blue, chromium oxide, chromium hydroxide, carbonblack, and composites thereof; and organic powders, such as polyamide,polyester, polyethylene, polypropylene, polystyrene, polyurethane, vinylresin, epoxy resin, polycarbonate resin, divinylbenzene/styrenecopolymer, copolymers consisting of more than one kind of monomer of theabove-described compounds, celluloid, acetylcellulose, cellulose,polysaccharides, protein, CI pigment yellow, CI pigment orange, and CIpigment green. The shape of powder can be any shape, for example, plate,agglomerate, scaly shape, sphere, porous sphere, and the particle sizeis also not limited in particular.

In the preparation of the surface-treated powder of the presentinvention, the surface treatment of the powder can be conducted by anynormal treatment method; thus, the method is not limited in particular.Examples of the treatment of the powder with the above-described polymerinclude the method in which the polymer is dissolved in a suitablesolvent such as ethyl alcohol, the powder is mixed into the solution andstirred, and then the solvent is removed; and the method in which apolymer dissolved in a non-volatile oil such as a higher alcohol isdirectly mixed into the powder with stirring. When the surface-treatedpowder of the present invention is blended into cosmetics, the polymermay be directly mixed, with stirring, into the powder base during theproduction process of the cosmetics.

In the present invention, when the powder is treated with theabove-described polymer, it is necessary to pay attention to the zetapotential of the powder. Here, the zeta potential of the powderindicates a difference between the potential of the outermost surface(sliding surface) of the moving layer, which is in close contact withthe solid phase, and the potential in the solution during the relativemovement of the solid phase and the liquid phase. When the solution isat near-neutral pH, the zeta potential of titanium oxide and silica isnegative; on the contrary, the zeta potential of zinc oxide and aluminais positive. When a powder with the positive zeta potential, such aszinc oxide or alumina, is treated with the normal method, the carboxylicacid site, which is important for pH response, is countered by thepositive charge of the powder surface. As a result, the obtainedsurface-treated powder may not exhibit a pH response. In order toprovide pH response capability to the powder, it is necessary to changethe zeta potential of the powder surface to be negative by treating thepowder surface with an inorganic compound or an organic compoundpossessing a negative charge, such as silica or polystyrene sulfonicacid. Examples of such a treatment method include the method in whichthe powder is dispersed in a water glass solution, and silica isdeposited on the surface by the dropwise addition of an acid; and themethod in which the powder is dispersed in an aqueous solution ofpolystyrene sulfonic acid, and water is evaporated.

In the surface-treated powder of the present invention, the mass ratioof the coated polymer to the powder (polymer:powder) is preferably 3:97to 40:60 and more preferably 5:95 to 30:70. If the amount of coatedpolymer is less than 3:97, desired characteristics may not be providedto the powder. If the amount of coated polymer is more than 40:60, thefeeling during the use of the cosmetics may be negatively affected.

The cosmetics of the present invention are characterized in that theabove obtained surface-treated powder is comprised in the cosmetics. Theblending amount of the surface-treated powder is preferably equal to ormore than 3 mass % of the total amount of cosmetics and more preferably5 to 95 mass %. If the blending amount is less than 3 mass %, the effectof the present invention may not be achieved.

To the cosmetics of the present invention, normally used cosmeticingredients, such as water, oil, powder (untreated), surfactant,fluorine compounds, resin, thickener, preservative, perfume, ultravioletabsorber, moisturizer, bioactive component, salts, solvent, antioxidant,chelating agent, neutralizing agent, and pH adjusting agent may beblended in addition to the above-described surface-treated powder so faras the effect of the present invention is not undermined.

The forms of cosmetics in the present invention are not limited inparticular. Their examples include makeup cosmetics such as foundation,white face powder, lipstick, eye shadow, cheek color, mascara, and eyeliner; sunscreen; foundation cream; and hair cream.

EXAMPLE 1

Examples of the present invention will hereinafter be described.However, the present invention is not limited by these examples.

Initially, the polymer synthesis methods of the present invention willbe described.

SYNTHESIS EXAMPLE 1 11-Methacrylamidoundecanoic acid (MAU) homopolymer

Into a mixed solvent of 32.4 mL of methanol and 3.6 mL water(methanol/water=9/1) were dissolved 5.244 g (18 mmol) of sodium11-methacrylamidoundecanoate (NaMAU) and 7.4 mg (0.045 mmol) ofazobisisobutyronitrile. The solution was deaerated by bubbling argon for30 minutes, the container was covered with a septum, and thepolymerization was conducted by heating the solution at 60° C. for 12hours. After the completion of the polymerization reaction, the reactionsolution was dropwise added into a large excess of ether, and theresulting precipitate was collected by filtration under suction. Thisprecipitate was dissolved in water, dialyzed against pure water for 1week, and 2.64 g of NaMAU homopolymer was obtained by freeze-drying(yield: 50.40%).

Into water was dissolved 1.10 g of the collected NaMAU homopolymer, andthe pH was adjusted to 4 with hydrochloric acid. This solution wasdialyzed against water of pH 5 for 1 week, and 0.97 g of11-methacrylamidoundecanoic acid (MAU) homopolymer was obtained byfreeze-drying.

SYNTHESIS EXAMPLE 2 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer(MAU/AMPS=95/5)

Into a mixed solvent of 32.4 mL of methanol and 3.6 mL water(methanol/water=9/1) were dissolved 4.9823 g (17.1 mmol) of sodium11-methacrylamidoundecanoate (NaMAU), 186.5 mg (0.9 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS), 39.6 mg (0.99 mmol) ofsodium hydroxide, and 7.4 mg (0.045 mmol) of azobisisobutyronitrile. Thesolution was deaerated by bubbling argon for 30 minutes, the containerwas covered with a septum, and the polymerization was conducted byheating the solution at 60° C. for 12 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ether, and the resulting precipitate was collected byfiltration under suction. This precipitate was dissolved in water,dialyzed against pure water for 1 week, and 2.78 g of random NaMAU/AMPScopolymer (95/5) was obtained by freeze-drying (yield: 53.71%).

Into water was dissolved 1.54 g of the collected NaMAU/AMPS copolymer,and the pH was adjusted to 4 with hydrochloric acid. This solution wasdialyzed against water of pH 5 for 1 week, and 0.97 g of random MAU/AMPScopolymer (95/5) was obtained by freeze-drying.

In the following section, the surface treatment method of powder withthe surface-treating agent of the present invention will be described.

POWDER TREATMENT EXAMPLE 1

Into 500 mL of ethanol were dissolved 45 g of a polymer prepared by theabove-described Synthesis Example 1 or Synthesis Example 2 and 15 g ofstearic acid. Into this solution was blended 240 g of titanium oxide anddispersed, and the ethanol was evaporated with an evaporator. Theobtained agglomerate was pulverized, and the surface-treated powder wasobtained.

The obtained treated powder was dissolved, by mixing, into a buffersolution of pH 5 and a buffer solution of pH 10 in a powder-solutionratio of 1:100. This solution was centrifuged to isolate the powder, andthe residual liquid was removed by drying. The obtained powder wasanalyzed by elemental analysis to measure the degree of polymer coating,and the content of polymer was found to be 15 mass % of the totalpowder, and the content of stearic acid was 5 mass % of the totalpowder.

EXAMPLES 1-1 TO 1-4 AND COMPARATIVE EXAMPLES 1-1 TO 1-4

In order to investigate the properties of the powder that has beensurface-treated with the polymer of the present invention, the presentinventors prepared titanium oxide powders that were surface-treated withvarious polymers according to the above-described Synthesis Example 1,Synthesis Example 2, and Powder Treatment Example 1. Then the presentinventors evaluated the water solubility of the treated powders underthe acidic (pH 5) and the basic (pH 10) conditions. In addition, similartests were conducted using silicones and acrylic acid/acrylic acid estercopolymer, which are traditional hydrophobizing surface-treating agents,as comparative examples. Evaluation results are shown in Table 1 andFIGS. 1 and 2. The evaluation method was as follows.

Water Solubility of Treated Powder

Each of 0.1 g titanium oxide powder that has been surface-treated withvarious surface-treating agents and a 30 mL aqueous buffer solution ofpH 5 or pH 10 were placed in a vial, mixed for 1 minute by stirring witha magnetic stirrer, and allowed to stand. Then the condition of eachsolution was checked. ∘: Powder evenly dissolved in water, and it formeda white cloudy solution. x: Powder did not dissolve in water, and itseparated on the water surface.

TABLE1 Water solubility of powder Surface-treating agent pH 5 pH 10Example 1-1 MAU/AMPS copolymer (MAU/AMPS = 90/10) X ◯ 1-2 MAU/AMPScopolymer (MAU/AMPS = 95/5) X ◯ 1-3 MAU/AMPS copolymer (MAU/AMPS = 99/1)X ◯ 1-4 MAU homopolymer (MAU/AMPS = 100/0) X ◯ Comperative 1-1Methylhydrogenpolysiloxane X X Example 1-2 Dimethyldichlorosilane X X1-3 Octyl acrylamide/acryl resin copolymer *1 X X 1-4 Vinylacetate/crotonic acid copolymer X X *1: Darmacryl-79 (Kanebo-NSC)

As shown in Table 1 and FIGS. 1 and 2, the surface-treated powder withMAU homopolymer or MAU/AMPS copolymer of the present invention (Examples1-1 to 1-4) did not dissolve in water under acidic condition (pH 5).Thus, the powder was found to have excellent hydrophobicity under acidiccondition (pH 5). On the other hand, under basic condition (pH 10), thetreated powder evenly dissolved in water. Thus, the powder was found tochange to hydrophilic under basic condition (pH 10). That is to say,when the powder treated with the polymer of the present invention isblended into cosmetics, the powder has excellent hydrophobicity in theacidic to neutral region, in which normal cosmetics are used; as aresult, the makeup is long-lasting. Nevertheless, the powder can beeasily rinsed away with water under the moderately basic condition thatis generated with soap because the powder surface changes tohydrophilic.

In contrast, the powder that is surface-treated with silicones oracrylic acid/acrylic acid ester copolymer, which is the traditionallyused hydrophobizing agent in cosmetic powder (Comparative Examples 1-1to 1-4), dissolved in water neither under acidic condition (pH 5) norunder basic condition (pH 10). Thus, when the powder treated with thetraditional surface-treating agent is blended in cosmetics, long-lastingmakeup could be achieved. However, it is difficult to rinse away withsoap water because excellent hydrophobicity is maintained even underbasic conditions.

SYNTHESIS EXAMPLE 3 3-{4-[(Methacryloxy)methyl]phenyl}acrylic acid(MMPA) homopolymer

1) Synthesis of MMPA Monomer

In 25 g of acetone were dissolved 2.46 g (15 mmol) of 4-hydroxycinnamicacid and 0.005 g of butylhydroxytoluene. To the solution was dropwiseadded 1.57 g (15 mmol) of methacryloyl chloride, and the mixture wasstirred at room temperature for 3 hours. After the completion of thereaction, to the solution was dropwise added 1.67 g of triethylamine,and then 100 g of 0.015N dilute hydrochloric acid solution was added.The resulting precipitate was collected by filtration under suction. Theprecipitate was washed with water and dried at 30° C. under reducedpressure, whereby 2.09 g of MMPA monomer was obtained (yield: 60%). Bythe NMR analysis of the product, the formation of MMPA monomer wasconfirmed. The NMR analysis results are shown in FIG. 3.

2) Polymerization of MMPA Monomer

In 100 g of tetrahydrofuran was dissolved 2.01 g (9 mmol) of theabove-obtained MMPA monomer, and nitrogen was bubbled through thesolution for 40 minutes. Subsequently, 0.038 g (0.23 mmol) ofazobisisobutyronitrile that was dissolved in 10 g of tetrahydrofuran wasdropwise added to the solution. After nitrogen was bubbled through thesolution for 10 minutes, the polymerization was conducted by stirring at60° C. for 24 hours. After the completion of the polymerizationreaction, the reaction solution was concentrated with an evaporator, andthe precipitate was removed by the addition of ethyl acetate. Thesolution was concentrated again with an evaporator. By drying at 30° C.under reduced pressure, 1.64 g of MMPA homopolymer was obtained (yield:82%).

POWDER TREATMENT EXAMPLE 2

In 50 mL of tetrahydrofuran was dissolved 1 g of MMPA homopolymer, whichwas prepared in the above-described Synthesis Example 3. In thissolution, 9 g of titanium oxide was blended and dispersed, andtetrahydrofuran was evaporated with an evaporator. The obtainedagglomerate was pulverized, whereby the surface-treated powder wasobtained.

EXAMPLE 1-5

The present inventors prepared titanium oxide powder that wassurface-treated with MMPA homopolymer according to the above-describedPowder Treatment Example 2. The obtained treated powder was blended anddispersed in buffer solutions of pH 5 and pH 10 in a powder-solutionratio of 1:100. Thus, the water solubility of the treated powder underacidic condition (pH 5) and basic condition (pH 10) was evaluated. Theresults are shown in FIG. 4.

As shown in FIG. 4, surface-treated powder with MMPA homopolymer of thepresent invention (Example 1-5) did not dissolve in water under acidiccondition (pH 5). On the other hand, under basic condition (pH 10), thetreated powder evenly dissolved in water. Thus, it was confirmed thatthe powder changed from hydrophobic to hydrophilic by the change of pH.

Subsequently, the present inventors conducted infrared spectroscopicmeasurement of the MMPA polymer of the above-described Synthesis Example3 under the condition of no treatment and under the condition of 1 MNaOH solution treatment. The results are shown in FIG. 5.

As shown in FIG. 5, the MMPA homopolymer of the present invention showspeaks due to carboxylic acid (—COOH) under the condition of notreatment. Under the condition of 1 M NaOH solution treatment, theabove-described peaks due to the carboxylic acid disappear, and theappearance of a new carboxylate ion (—COO⁻) peak was identified.According to the results, the polymer of the present invention is in theform of hydrophobic carboxylic acid under acidic to neutral conditions,and it changes to the hydrophilic carboxylate ion under basicconditions. As a result, the pH-responsive hydrophobicity-hydrophilicitychange is considered to take place.

EXAMPLE 2

The present inventors prepared cosmetics in which the surface-treatedpowder with the polymer of the present invention is blended, and theevaluation was conducted.

EXAMPLE 2-1

In 1000 mL of ethanol were dissolved 34.5 g of the MAU/AMPS copolymer(MAU/AMPS=95/5), which was prepared according to the above-describedSynthesis Example 2, and 34.5 g of stearic acid. In this solution, 85 gof talc, 50.8 g of sericite, 10 g of titanium oxide, 6 g of nylonpowder, 0.4 g of black iron oxide, 5.8 g of yellow iron oxide, and 2 gof red iron oxide were blended and dispersed, and the ethanol wasevaporated with an evaporator. The obtained agglomerate was pulverized,and the surface-treated powder of Example 2-1 was obtained.

EXAMPLE 2-2

Powder type foundation Amount (mass %) (1)Surface treated powder inExample 2-1 86.6 (2)Liquid paraffin 4.0 (3)Octyldodecyl myristate 3.0(4)Sorbitan isostearate 3.0 (5)Octyldodecanol 3.0 (6)Preservative 0.1(7)Disinfectant 0.1 (8)Antioxidant 0.1 (9)Perfume 0.1(Manufacturing method) (2)-(6) are heated and dissolved, then (1),(7)-(9) are added thereto. This was mixed with Henschel mixer, thepowder type foundation was obtained.

Above obtained powder type foundation was excellent in long-lasting, andable to be easily rinsed away with water by using soap.

EXECUTION EXAMPLE 2-3

Two-layers type W/O sunscreen Amount (mass %)  (1)Talc 10.0  (2)Surfacetreated titania in Example 1-1 10.0  (3)Isocetyl octate 5.0 (4)Decamethylcyclopentasiloxane 26.8  (5)Dimethylpolysiloxane 10.0 (6)POE modified dimethylpolysiloxane 2.0  (7)Ion-exchanged water 28.0 (8)1,3-Butylene glycol 8.0  (9)Preservative 0.1 (10)Perfume 0.1(Manufacturing method) (3)-(6) were heated and mixed at 70° C. as oilphase. Separately, (8) and (9) were dissolved into (7) as aqueous phase.The powder of (1) and (2) was added into the oil phase, and dispersedwith the homomixer. The aqueous phase was added into this, andemulsified with the homo mixer. In addition, (10) was mixed with them,and filled into the container.

Above obtained two-layers type W/O sunscreen was excellent inlong-lasting, and able to be easily rinsed away with water by usingsoap.

EXAMPLE 2-4

W/O type foundation Amount (mass %) (1) Surface treated powder inExample 2-1 20.32 (2)Liquid paraffin 5.0 (3)Decamethylcyclopentasiloxane29.0 (4)POE modified dimethylpolysiloxane 4.5 (5)Ion-exchanged water36.0 (6)1,3-Butylene glycol 5.0 (7)Preservative 0.1 (8)Perfume 0.08(Manufacturing method) (2)-(4) were heated and dissolved at 70-80° C.(This was oil phase). (6) and (7) were dissolved into (5) (This wasaqueous phase). The oil phase was added into (1), and mixed withhomomixer. (8) was mixed with them, and water was added thereto. Thiswas filled it to the container.

Above obtained W/O type foundation was excellent in long-lasting, andable to be easily rinsed away with water by using soap.

EXAMPLE 2-5

Lipstick Amount (mass %)  (1)Surface treated titania in Example 1-3 10.0 (2)Red pigment No. 201 0.6  (3)Red pigment No. 202 1.0  (4)Red pigmentNo. 223 0.2  (5)Candelilla wax 9.0  (6)Solid paraffin 8.0  (7)Beeswax5.0  (8)Carnauba wax 5.0  (9)Lanolin 11.0 (10)Castor oil 23.2 (11)Cetyl2-ethylhexanoate 17.0 (12)Isopropyl myristic acid ester 10.0(13)Antioxidant q.s. (14)Perfume q.s.(Manufacturing method) (1)-(3) were mixed with a part of (10), andtreated with a roller (This was pigment part). (4) were dissolved into apart of (10) (This was dye part). (5)-(13) were mixed, heated anddissolved, then the pigment part and dye part were added thereto. Thesewere dispersed uniformly with homomixer. This was poured in mold, cooledquickly, and shaped as stick.

Above obtained lipstick was excellent in long-lasting, and able to beeasily rinsed away with water by using soap.

EXAMPLE 2-6

Oil type stick foundation Amount (mass %) (powder part) (1)Surfacetreated powder in Example 2-1 50.0 (Oil phase) (2)Solid paraffin 3.0(3)Microcrystalline Wax 7.0 (4)Petrolatum 15.0 (5)Dimethylpolysiloxane3.0 (6)Squalane 5.0 (7)Isopropyl palmitate 17.0 (8)Antioxidant q.s.(9)Perfume q.s.(Manufacturing method) (2)-(8) were dissolved at 85° C., and enoughmixed powder part were added thereto with stirring. Next, this wasdispersed by grinding with colloid mill. (9) was added thereto. Afterdegassing, this was poured into the container at 70° C. This was cooled,and the cosmetic was obtained.

Above obtained stick foundation was excellent in long-lasting, and ableto be easily rinsed away with water by using soap.

EXAMPLE 3

The present invention will hereinafter be described in further detail byother examples. However, the present invention is not limited by theseexamples. The molecular weight was determined with size exclusionchromatography, HLC-8220 GPC (Tosoh Corporation). As the column, ShodexAsahipak GF-7M HQ (Showa Denko K.K.) was used, and as the mobile phase,methanol containing 100 mM of lithium perchlorate was used. As thestandard material, polyethylene oxide was used, and the obtained weightaverage molecular weight is based on polyethylene oxide.

EXAMPLE 3-1 11-Methacrylamidoundecanoic acid (MAU) homopolymer

In 224.69 g of methanol were dissolved 75.0 g (278.49 mmol) of11-methacrylamidoundecanoic acid (MAU) and 0.31 g (1.89 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 45.6 g of MAU homopolymerwas obtained (yield: 60.8%). The weight average molecular weight was66000.

EXAMPLE 3-2 11-Methacrylamidoundecanoic acid (MAU) homopolymer

In 224.07 g of methanol were dissolved 75.0 g (278.49 mmol) of11-methacrylamidoundecanoic acid (MAU) and 0.93 g (5.66 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 64.9 g of MAU homopolymerwas obtained (yield: 86.5%). The weight average molecular weight was61000.

EXAMPLE 3-3 12-Methacrylamidododecanoic acid (MAD) homopolymer

In 120.0 g of methanol was dissolved 40.0 g (141.34 mmol) of12-methacrylamidododecanoic acid (MAD) and 0.58 g (3.53 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 124.15 g of MAD homopolymer was obtained (yield: 60.4%). Theweight average molecular weight was 33000.

EXAMPLE 3-4 12-Acrylamidododecanoic acid (AAD) homopolymer

In 360.0 g of methanol were dissolved 40.0 g (148.70 mmol) of12-acrylamidododecanoic acid (AAD) and 0.61 g (3.71 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 27.51 g of AAD homopolymer was obtained (yield: 68.8%). Theweight average molecular weight was 44000.

EXAMPLE 3-5 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)

In 223.92 g of methanol were dissolved 74.23 g (275.63 mmol) of11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 0.93 g (5.66 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of diethylether, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 52.0 g of random MAU/AMPScopolymer (99/1) was obtained (yield: 69.2%). The weight averagemolecular weight was 56000.

EXAMPLE 3-6 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)

In 223.30 g of methanol were dissolved 74.23 g (275.63 mmol) of11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 1.55 g (9.44 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 52.3 g of random MAU/AMPScopolymer (99/1) was obtained (yield: 69.6%). The weight averagemolecular weight was 36000.

EXAMPLE 3-7 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)

In 236.75 g of methanol were dissolved 74.23 g (275.63 mmol) of11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 3.10 g (18.88 mmol)of azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 60.1 g of random MAU/AMPScopolymer (99/1) was obtained (yield: 80.0%). The weight averagemolecular weight was 21000.

EXAMPLE 3-8 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (90/10)

In 59.4 g of methanol were dissolved 18.42 g (68.41 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.58 g (7.60 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.31 g (7.60 mmol) of sodium hydroxide, and 0.31 g (1.89 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 17.8 g of random MAU/AMPScopolymer (90/10) was obtained (yield: 87.9%). The weight averagemolecular weight was 92000.

EXAMPLE 3-9 11-Methacrylamidoundecanoic acid(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)

A polymerization inhibitor comprised in MAU was removed by dissolving11-methacrylamidoundecanoic acid (MAU) in chloroform and passing thesolution through an inhibitor remover disposable column (AldrichChemical). In 59.91 g of methanol were dissolved 19.85 g (73.69 mmol) ofMAU without the polymerization inhibitor, 0.15 g (0.74 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.03 g (0.74 mmol) of sodium hydroxide, and 0.06 g (0.37 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction, thereaction solution was dropwise added into a large excess of ethylacetate, and the resulting precipitate was collected by filtration undersuction. After drying under reduced pressure, 17.33 g of random MAU/AMPScopolymer (99/1) was obtained (yield: 86.6%). The weight averagemolecular weight was 740000.

EXAMPLE 3-10 11-Methacrylamidoundecanoic acid (MAU)/potassium3-methacryloxypropanesulfonate copolymer (90/10)

In 59.69 g of methanol were dissolved 18.15 g (67.41 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.85 g (7.49 mmol) of potassium3-methacryloxypropanesulfonate (Tokyo Chemical industry Co.), and 0.31 g(1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Thesolution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 18.47 g of random MAU/potassium 3-methacryloxypropanesulfonatecopolymer (90/10) was obtained (yield: 92.4%). The weight averagemolecular weight was 240000.

EXAMPLE 3-11 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (99/1)

In 60.0 g of methanol were dissolved 19.85 g (70.14 mmol) of12-methacrylamidododecanoic acid (MAD), 0.15 g (0.72 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.028 g (0.70 mmol) of sodium hydroxide, and 0.29 g (1.77 mmol)of azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 13.5 g of random MAD/AMPS copolymer (99/1) was obtained(yield: 67.5%). The weight average molecular weight was 49000.

EXAMPLE 3-12 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (90/10)

In 60.0 g of methanol were dissolved 18.50 g (65.37 mmol) of12-methacrylamidododecanoic acid (MAD), 1.50 g (7.24 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.29 g (7.25 mmol) of sodium hydroxide, and 0.30 g (1.83 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 15.2 g of random MAD/AMPS copolymer (90/10) was obtained(yield: 75.1%). The weight average molecular weight was 50000.

EXAMPLE 3-13 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (80/20)

In 60.0 g of methanol were dissolved 16.90 g (59.72 mmol) of12-methacrylamidododecanoic acid (MAD), 3.10 g (14.96 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.60 g (1.50 mmol) of sodium hydroxide, and 0.31 g (1.89 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 16.1 g of random MAD/AMPS copolymer (80/20) was obtained(yield: 78.6%). The weight average molecular weight was 95000.

EXAMPLE 3-14 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (70/30)

In 60.0 g of methanol were dissolved 15.22 g (53.78 mmol) of12-methacrylamidododecanoic acid (MAD), 4.78 g (23.06 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 0.92 g (23.0 mmol) of sodium hydroxide, and 0.32 g (1.95 mmol) ofazobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 19.0 g of random MAD/AMPS copolymer (70/30) was obtained(yield: 91.6%). The weight average molecular weight was 108000.

EXAMPLE 3-15 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (60/40)

In 60.0 g of methanol were dissolved 13.44 g (47.49 mmol) of12-methacrylamidododecanoic acid (MAD), 6.56 g (31.65 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 1.27 g (31.75 mmol) of sodium hydroxide, and 0.32 g (1.95 mmol)of azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was drop wise added intoa large excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 20.05 g of random MAD/AMPS copolymer (60/40) was obtained(yield: 95.4%). The weight average molecular weight was 129000.

EXAMPLE 3-16 12-Methacrylamidododecanoic acid(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (50/50)

In 60.0 g of methanol were dissolved 11.55 g (40.81 mmol) of12-methacrylamidododecanoic acid (MAD), 8.45 g (40.77 mmol) of2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich JapanK.K.), 1.63 g (40.75 mmol) of sodium hydroxide, and 0.33 g (1.97 mmol)of azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 20.95 g of random MAD/AMPS copolymer (50/50) was obtained(yield: 98.4%). The weight average molecular weight was 176000.

EXAMPLE 3-17 11-Methacrylamidoundecanoic acid (MAU)/2-ethylhexylacrylate copolymer (90/10)

In 59.69 g of methanol were dissolved 18.59 g (69.02 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.41 g (7.67 mmol) of2-ethylhexyl acrylate (Sigma-Aldrich Japan K.K.), and 0.31 g (1.89 mmol)of azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution wasdeaerated by bubbling nitrogen for 60 minutes. The container was coveredwith a septum, and the polymerization was conducted by heating at 60° C.for 20 hours. After the completion of the polymerization reaction,yellow candy-like material was obtained. To this was added 80 g ofmethanol, and the material was dissolved. The obtained solution wasdropwise added into a large excess of ethyl acetate, and the resultingprecipitate was collected by filtration under suction. After dryingunder reduced pressure, 13.01 g of random MAU/2-ethylhexyl acrylatecopolymer (90/10) was obtained (yield: 65.0%). The weight averagemolecular weight was 560000.

EXAMPLE 3-18 11-Methacrylamidoundecanoic acid (MAU)/2,2,2-trifluoroethylacrylate copolymer (90/10)

In 59.68 g of methanol were dissolved 18.80 g (69.82 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.20 g (7.76 mmol) of2,2,2-trifluoroethyl acrylate (Tokyo Chemical industry Co.), and 0.32 g(1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Thesolution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 9.02 g of random MAU/2,2,2-trifluoroethyl acrylate copolymer(90/10) was obtained (yield: 45.1%). The weight average molecular weightwas 35000.

EXAMPLE 3-19 11-Methacrylamidoundecanoic acid(MAU)/2,2,3,3-tetrafluoropropyl methacrylate copolymer (90/10)

In 59.69 g of methanol were dissolved 18.47 g (68.60 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.53 g (7.62 mmol) of2,2,3,3-tetrafluoropropyl methacrylate (Tokyo Chemical industry Co.),and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).The solution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 16.15 g of random MAU/2,2,3,3-tetrafluoropropyl methacrylatecopolymer (90/10) was obtained (yield: 80.8%). The weight averagemolecular weight was 220000.

EXAMPLE 3-20 11-Methacrylamidoundecanoic acid(MAU)/2-(N,N-dimethylamino)ethyl acrylate copolymer (90/10)

In 59.68 g of methanol were dissolved 18.88 g (70.12 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.12 g (7.79 mmol) of2-(N,N-dimethylamino)ethyl acrylate (Tokyo Chemical industry Co.), and0.32 g (1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Thesolution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the solution was concentrated to dryness underreduced pressure, and the solid was dissolved in 60 g ofdimethylformamide. The obtained solution was dropwise added into a largeexcess of diethyl ether, and the resulting precipitate was collected byfiltration under suction. After drying under reduced pressure, 5.22 g ofrandom MAU/2-(N,N-dimethylamino)ethyl acrylate copolymer (90/10) wasobtained (yield: 26.1%). The weight average molecular weight was 130000.

EXAMPLE 3-21 11-Methacrylamidoundecanoic acid (MAU)/2-dimethylaminoethylmethacrylate copolymer (90/10)

In 59.68 g of methanol were dissolved 18.78 g (69.74 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.22 g (7.75 mmol) of2-dimethylaminoethyl methacrylate (Tokyo Chemical industry Co.), and0.32 g (1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Thesolution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the solution was concentrated to dryness underreduced pressure, and the solid was dissolved in 60 g ofdimethylformamide. The obtained solution was dropwise added into a largeexcess of diethyl ether, and the resulting precipitate was collected byfiltration under suction. After drying under reduced pressure, 7.78 g ofrandom MAU/2-dimethylaminoethyl methacrylate copolymer (90/10) wasobtained (yield: 38.9%). The weight average molecular weight was 250000.

EXAMPLE 3-22 12-Methacrylamidododecanoic acid(MAD)/N-hydroxyethylacrylamide (HEAA) copolymer (90/10)

In 60.0 g of methanol were dissolved 19.14 g (67.63 mmol) of12-methacrylamidododecanoic acid (MAD), 0.86 g (7.51 mmol) ofN-hydroxyethylacrylamide (HEAA: Kohjin Co., Ltd.), and 0.33 g (1.97mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,azobisisobutyronitrile was recrystallized from methanol in the usualway. The solution was deaerated by bubbling argon for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the reaction solution was dropwise added into alarge excess of diethyl ether, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 16.90 g of MAD/HEAA copolymer (90/10) was obtained (yield:84.5%).

EXAMPLE 3-23 11-Methacrylamidoundecanoic acid(MAU)/N,N-dimethylaminoethyl acrylate methyl chloride copolymer (90/10)

In 59.69 g of methanol were dissolved 18.52 g (68.77 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.48 g (7.64 mmol) ofN,N-dimethylaminoethyl acrylate methyl chloride (Kohjin Co., Ltd.), and0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Thesolution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the obtained solution was dropwise added into alarge excess of acetone, and the resulting precipitate was collected byfiltration under suction. After drying under reduced pressure, 9.43 g ofrandom MAU/N,N-dimethylaminoethyl acrylate methyl chloride copolymer(90/10) was obtained (yield: 47.2%). The weight average molecular weightwas 68000.

EXAMPLE 3-24 11-Methacrylamidoundecanoic acid(MAU)/N,N-dimethylaminopropylacrylamide methyl chloride copolymer(90/10)

In 59.69 g of methanol were dissolved 18.43 g (68.43 mmol) of11-methacrylamidoundecanoic acid (MAU), 1.57 g (7.60 mmol) ofN,N-dimethylaminopropylacrylamide methyl chloride (Kohjin Co., Ltd.),and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).The solution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, the obtained solution was dropwise added into alarge excess of acetone, and the resulting precipitate was collected byfiltration under suction. After drying under reduced pressure, 9.60 g ofrandom MAU/N,N-dimethylaminopropylacrylamide methyl chloride copolymer(90/10) was obtained (yield: 48.0%). The weight average molecular weightwas 42000.

EXAMPLE 3-25 11-Methacrylamidoundecanoic acid (MAU)/methoxypolyethyleneglycol monomethacrylate copolymer (90/10)

In 59.70 g of methanol were dissolved 17.96 g (66.67 mmol) of11-methacrylamidoundecanoic acid (MAU), 2.04 g (7.41 mmol) ofmethoxypolyethylene glycol monomethacrylate (Blenmer PME-200: Nippon Oil& Fats Co.), and 0.30 g (1.83 mmol) of azobisisobutyronitrile (NacalaiTesque, Inc.). The solution was deaerated by bubbling nitrogen for 60minutes. The container was covered with a septum, and the polymerizationwas conducted by heating at 60° C. for 20 hours. After the completion ofthe polymerization reaction, the obtained solution was dropwise addedinto a large excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 9.69 g of random MAU/methoxypolyethyleneglycol-monomethacrylate copolymer (90/10) was obtained (yield: 48.5%).The weight average molecular weight was 110000.

EXAMPLE 3-26 11-methacrylamidoundecanoic acid (MAU)/methoxypolyethyleneglycol monomethacrylate copolymer (99/1)

In 59.70 g of methanol were dissolved 19.80 g (73.50 mmol) of11-methacrylamidoundecanoic acid (MAU), 0.20 g (0.74 mmol) ofmethoxypolyethylene glycol monomethacrylate (Blenmer PME-200: Nippon Oil& Fats Co.), and 0.30 g (1.83 mmol) of azobisisobutyronitrile (NacalaiTesque, Inc.). The solution was deaerated by bubbling nitrogen for 60minutes. The container was covered with a septum, and the polymerizationwas conducted by heating at 60° C. for 20 hours. After the completion ofthe polymerization reaction, the obtained solution was dropwise addedinto a large excess of ethyl acetate, and the resulting precipitate wascollected by filtration under suction. After drying under reducedpressure, 10.28 g of random MAU/methoxypolyethylene glycolmonomethacrylate copolymer (99/1) was obtained (yield: 51.4%). Theweight average molecular weight was 34000.

EXAMPLE 3-27 11-Methacrylamidoundecanoic acid(MAU)/methacryloxy-modified silicone copolymer (90/10)

In a mixed solution of 30 g of methanol and 30 g of chloroform weredissolved 14.16 g (52.57 mmol) of 11-methacrylamidoundecanoic acid(MAU), 5.84 g (5.84 mmol) of methacryloxy-modified silicone (FM-0711:Chisso Corporation), and 0.24 g (1.46 mmol) of azobisisobutyronitrile(Nacalai Tesque, Inc.). The solution was deaerated by bubbling nitrogenfor 60 minutes. The container was covered with a septum, and thepolymerization was conducted by heating at 60° C. for 20 hours. Afterthe completion of the polymerization reaction, the solution wasconcentrated to dryness under reduced pressure, and the solid wasdissolved in 100 g of tetrahydrofuran. The obtained solution wasdropwise added into a large excess of n-hexane, and the resultingprecipitate was collected by filtration under suction. After dryingunder reduced pressure, 12.15 g of random MAU/methacryloxy-modifiedsilicone copolymer (90/10) was obtained (yield: 60.8%). The weightaverage molecular weight was 53000.

EXAMPLE 3-28 11-Methacrylamidoundecanoic acid (MAU)/2-methacryloxyethylphosphoric acid copolymer (90/10)

In a mixed solvent of 75 g of methanol and 25 g of ion-exchanged waterwere dissolved 18.40 g (68.32 mmol) of 11-methacrylamidoundecanoic acid(MAU), 1.60 g (7.59 mmol) of 2-methacryloxyethyl phosphoric acid(Phosmer-M: Uni-Chemical Co.), 0.30 g (7.59 mmol) of sodium hydroxide,and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).The solution was deaerated by bubbling nitrogen for 60 minutes. Thecontainer was covered with a septum, and the polymerization wasconducted by heating at 60° C. for 20 hours. After the completion of thepolymerization reaction, a gelatinous product was obtained. This productwas dried under reduced pressure, and 6.0 g of the dried material wasadded to 200 g of methanol. After sufficient stirring, insolublematerial was removed by filtration. The obtained solution was dropwiseadded into a large excess of ethyl acetate, and the resultingprecipitate was collected by filtration under suction. After dryingunder reduced pressure, 2.01 g of random MAU/2-methacryloxyethylphosphoric acid copolymer (90/10) was obtained. The weight averagemolecular weight was 190000.

EXAMPLE 4

In the following section are shown formulation examples of cosmetics inwhich the powders treated with various surface-treating agents describedin the above examples are blended.

EXAMPLE 4-1 Powder solid foundation mass % Dimethylpolysiloxane 5Isostearic acid 0.5 Diisostearyl malate 1 Glyceryl tri2-ethylhexanoate 3Sorbitan sesquiisostearate 1 Spherical PMMA coated mica 4 Fineparticlezinc oxide 1 Fineparticle titanium oxide 3 Synthetic phlogopite 1Metallic soap treated talc Balance Spheric silica 3 Red iron oxidecoated titanated mica 1 Anhydrous silicic acid coated mica 6DL-alpha-tocopherol acetate 0.1 D-sigma-tocopherol 0.1 Ethylparaben q.s.Methyl bis(trimethylsiloxy)silylisopentyl trimethoxycinnamate 0.12-Ethylhexyl p-methoxycinnamate 3 Spheric polyalkylacrylate powder 2Polyalkylacrylate powder including liquid paraffin 4 Treated talc withExample 3-13 *1 20 Treated sericite with Example 3-13 *2 15 Treatedtitania with Example 3-13 *1 10 Treated yellow iron oxide (coloringmaterial) 4.2 with Example 3-13 *1 Treated red iron oxide (coloringmaterial) 0.7 with Example 3-13 *1 Treated black iron oxide (coloringmaterial) 0.1 with Example 3-13 *1 *1 Powder:Polymer = 80:20(mass %) *2Powder:Polymer = 75:25(mass %)

EXAMPLE 4-2 Powder solid foundation mass % Alpha-olefine oligomer 3Petrolatum 2 Synthetic hydrocarbon wax powder 2 Dimethylpolysiloxane 3Isostearic acid 1 Glyceryl tri2-ethylhexanoate 3 Sorbitansesquiisostearate 1 Glycerol modified silicone resin coated talc 5Treated synthetic phlogopite with Example 3-18 *3 27 Treated titaniawith Example 3-18 *4 5 Boron nitride 1 Treated sericite with Example3-18 *3 20 Treated talc with Example 3-18 *3 Balance Treated mica withExample 3-18 *4 5 Treated barium sulfate with Example 3-18 *4 1 Red ironoxide coated titanated mica 0.1 DL-alpha-tocopherol acetate 0.1D-delta-tocopherol 0.1 Parahydroxybenzoic acid ester q.s Red iron oxidecoated titanated mica q.s Treated yellow iron oxide with Example 3-18 *3q.s Treated black iron oxide with Example 3-18 *3 q.s Nylon powder 2Silicic anhydride 2 Spheric polyalkylacrylate powder 6 *3 Powder:Polymer= 80:20(mass %) *4 Powder:Polymer = 75:25(mass %)

EXAMPLE 4-3 Powder solid foundation mass % Synthetic hydrocarbon waxparticle 2 Dimethylpolysiloxane 6 Purified lanolin 5 Glyceryl tri2-ethylhexanoate 2 Sorbitan sesquiisostearate 0.5 Treated needle-shapefineparticle titania with Example 3-12 *5 5 Treated fineparticle zincoxide with Example 3-12 *5 1 Treated iron oxide/titania sinteredmaterial 7 with Example 3-12 *6 Treated barium sulfate with Example 3-12*5 8 Treated sericite carcined material with Example 3-12 *6 BalanceTitanium-deoxided titanated mica pearl pigments 2 Treated syntheticphlogopite with Example 3-18 *6 5 Treated talc with Example 3-12 *6 2Spheric silica 3 Treated mica with Example 3-12 *6 15 Stearylglycyrrhetate 0.1 Ascorbyl dipalmitate 0.1 DL-alpha-tocopherol acetate0.1 D-delta-tocopherol 0.1 Parahydroxybenzoic acid ester q.s. Ethylhexylmethoxycinnamate 3 Treated red iron oxide with Example 3-12 *6 1 Treatedyellow iron oxide in Example 3-12 *6 1 Treated black iron oxide inExample 3-12 *6 1 Spheric polyalkyl acrylate 3 Perfume q.s. *5Powder:Polymer = 85:15(mass %) *6 Powder:Polymer = 75:25(mass %)

EXAMPLE 4-4 Powder solid foundation mass % Alpha-olefine oligomer 10Microcrystalline wax 0.5 Ceresin 5 Dimethylpolysiloxane 15 Methylphenylpolysiloxane 10 Macadamia nuts oil 0.1 Carnauba wax 0.1 Glyceryltri2-ethylhexanoate 7 Cetyl 2-ethylhexanoate 10 Sorbitansesquiisostearate 1.5 Treated mica with Example 3-1 0.5 Aluminumstearate 1 Cross-linked silicone powder (Trefil E-506) 8N-Lauroyl-L-lisine 0.1 D-delta-tocopherol q.s. Treated red iron oxidewith Example 3-2 + behenyl alcohol q.s. Treated yellow iron oxide withExample 3-2 + behenyl alcohol q.s. Calcium alginate powder 1 Nylonpowder Balance Treated spherical anhydrous silicic acid 1 with Example3-2 + behenyl alcohol Treated titania with Example 3-2 + behenyl alcohol1 *Powder:Polymer:Behenyl alcohol = 75:20:5(mass %)

EXAMPLE 4-5 Powder solid foundation mass % Microcrystalline wax 5Dimethylpolysiloxane 10 Decamethylcyclopentasiloxane 30Polyoxyethylene/methylPolysiloxane copolymer 2 Dipropylene glycol 3Palmitic acid 0.5 Sorbitan sesquiisostearate 1 Treated yellow iron oxidewith Example 3-9 + isostearic acid *7 3 Treated red iron oxide Example3-9 + isostearic acid *7 1 Treated black iron oxide with Example 3-9 +isostearic acid *7 q.s. Treated anhydrous silicic acid 2 with Example3-9 + isostearic acid *8 Treated titania with Example 3-9 + isostearicacid *7 15 Treated sericite with Example 3-9 + isostearic acid *8 10Treated titania/red iron oxide coated mica 3 with Example 3-9 +isostearic acid *8 Cross-linked silicone powder (Trefil E-506) 3N-Lauroyl-L-lisine 0.1 Tocopheryl acetate 0.1 Delta-tocopherol 0.1Parahydroxybenzoic acid ester q.s. Melilot extract 2 Purified waterBalance *7 Powder:Polymer:Isostearic acid = 75:20:5(mass %) *8Powder:Polymer:Isostearic acid = 75:45:10(mass %)

EXAMPLE 4-6 Powder solid foundation mass % Microcrystalline Wax 1Dimethylpolysiloxane 15 Decamethylcyclopentasiloxane 2 1,3-Butyleneglycol 6 Candelilla wax 3 Isostearic acid 1 Ethylene glycol fatty acidester 0.1 Octyldodecyl lanolate 0.52-alkyl-N-carboxymethy-N-hydroxyethylimidazolinium betaine 4 Treatedpigment class titania with Example 3-21 7.5 Treated barium sulfate withExample 3-21 5 Treated fineparticle titania with Example 3-21 7 Treatedtalc with Example 3-21 3 Treated silicic anhydrid with Example 3-21 4Cross-linked silicone powder (Trefil E-506) 0.1 Sodium metaphosphate 0.1Hydroxypropyl cyclodextrin 0.1 DL-alpha-tocopherol acetate 0.1 Hamamelisextract 0.1 Peony root extract 0.1 Sodium chondroitin sulphate 0.1Sodium hyaluronate 0.1 Parahydroxybenzoic acid ester q.s. Treated rediron oxide with Example 3-21 q.s. Treated yellow iron oxide with Example3-21 q.s. Treated black iron oxide with Example 3-21 q.s. Xanthan gum0.2 Carboxymethyl cellulose sodium 0.2 Melilot extract 2 Purified waterBalance *Powder:Polymer = 75:25(mass %)

EXAMPLE 4-7 Powder solid foundation mass % Ceresin 5Dimethylpolysiloxane 10 Decamethylcyclopentasiloxane 10Dodecamethylcyclohexasiloxane 20 Carnauba wax 0.5 Candelilla wax 0.5Glyceryl tri2-ethylhexanoate Balance Sorbitan sesquiisostearate 1.5Treated titania with Example 3-3 8 Treated kaolin with Example 3-3 10Treated mica with Example 3-3 12 Titanated mica/polyalkylacrylatecomposite powder 1 Polyalkylacrylate coated titanated mica 1Treated titania MT-014TV with Example 3-3 5 Treated black iron oxidecoated titanated mica 0.5 with Example 3-3 Tocopheryl acetate 0.1Delta-tocopherol 0.1 Treated red iron oxide with Example 3-3 q.s.Treated yellow iron oxide with Example 3-3 q.s. Treated iron blue withzinc oxide q.s. Treated black iron oxide with Example 3-3 q.s. Perfumeq.s. *Powder:Polymer = 75:25(mass %)

EXAMPLE 4-8 Powder solid foundation mass % Dimethylpolysiloxane 15Decamethylcyclopentasiloxane 20 Polyoxyethylene/methylpolysiloxanecopolymer 5 High moleculer weight amino modified silicone 0.1 Glycerin 51,3-Butylene glycol 10 Palmitic acid 0.5 Cholesteryl macadamiate 0.1Distearyldimethylammonium chloride 0.2 Treated yellow iron oxide withExample 3-19 2 Treated red iron oxide with Example 3-19 1 Treated blackiron oxide with Example 3-19 0.3 Treated titania with Example 3-19 10Treated talc with Example 3-19 1.5 Treated spindle-shape titania withExample 3-19 3 L-sodium glutamate 0.5 DL-alpha-tocopherol acetate 0.1Parahydroxybenzoic acid ester q.s. Methylbis(trimethylsiloxy)sirylisopentil 0.1 trimethoxycinnamateDimethyldistearylammonium hectorite 1.5 Spheric nylon powder 1 Purifiedwater Balance Perfume q.s. *Powder:Polymer = 75:25(mass %)

EXAMPLE 4-9 Powder solid foundation mass % Dimethylpolysiloxane 3Decamethylcyclopentasiloxane 15 Polyoxyethylene/methylpolysiloxanecopolymer 3 Glycerin 3 1,3-Butylene glycol 5 Palmitic acid 0.5Distearyldimethylammonium chloride 0.2 Glycerol modified silicone resincoated sericite 0.5 Treated yellow iron oxide coated titanated mica 0.5with Example 3-11 *9 Treated titania with Example 3-11 *9 2 Treated ironoxide/titania sintered material (PK) 12 with Example 3-11 *10 Treatedtalc with Example 3-11 *9 10 Treated titania coated sericite withExample 3-11 *10 0.5 Boron nitride 0.5 Fineparticle titanium oxide 0.5Treated red iron oxide coated titanated mica 0.5 with Example 3-11 *10Phytosterol 0.1 L-sodium glutamate 1.5 Ascorbyl dipalmitate 0.1DL-alpha-tocopherol acetate 0.1 Acetylated sodium hyaluronate 0.1Parahydroxybenzoic acid ester q.s. Phenoxyethanol q.s. Red iron oxidecoated titanated mica 0.5 Treated yellow iron oxide with Example 3-11 *92 Treated black iron oxide with Example 3-11 *9 0.2 Spheric nylon powder1 Purified water Balance Perfume q.s. *9 Powder:Polymer = 80:20(mass %)*10 Powder:Polymer = 75:25(mass %)

EXAMPLE 4-10 Powder solid foundation mass % Behenyl alcohol 0.5Dipropylene glycol 6 Stearic acid 1 Glyceryl monostearate 1 Potassiumhydroxide 0.2 Triethanolamine 0.8 DL-alpha-tocopherol acetate 0.1Parahydroxybenzoic acid ester q.s. Treated yellow iron oxide withExample 3-4 1 Alpha-olefine oligomer 3 Dimethylpolysiloxane (6 mPa · s)2 Dimethylpolysiloxane (100 mPa · s) 5 Batylalcohol 0.5 Isostearic acid1 Behenic acid 0.5 Cetyl 2-ethylhexanoate 10 Polyoxyethylene glycerinmonostearate 1 Treated titania with Example 3-4 3 Titanatedmica/polyalkyl acrylate composite powder 0.5 Treated fineparticletitania with Example 3-4 10 Polyalkylacrylate coated titanated mica 0.5Treated black iron oxide coated titanated mica in Example 3-4 0.5Treated silicic anhydride with Example 3-4 6 2-Ethylhexylp-methoxycinnamate 2 Treated red iron oxide with Example 3-4 q.s.Treated iron blue with Example 3-4 q.s. Treated black iron oxide withExample 3-4 q.s. Legal coloring pigment q.s. Xanthan gum 0.1 Bentonite 1Sodium carboxymethylcellulose 0.1 Purified water Balance Perfume q.s.*Powder:Polymer = 85:15(mass %)

EXAMPLE 4-11 Powder solid foundation mass %Dodecamethylcyclohexasiloxane 15 Decamethylcyclopentasiloxane Balance3-Tris(trimethylsiloxy) silylpropyl carbamoyl pullulan 3 Ethanol 10Isostearic acid 0.5 Treated zinc oxide with Example 3-11 0.5 Treatedtitania with Example 3-12 10 Treated talc with Example 3-12 7 Treatedfineparticle titania with Example 3-12 5 Cross-linked silicone powder 1Spheric silicic anhydride 2 Magnesium ascorbyl phosphate 0.2DL-alpha-tocopherol acetate 0.1 D-delta-tocopherol 0.1 Glutathione 0.1Sophora Extract 0.1 2-Ethylhexyl p-methoxycinnamate 5 Treated red ironoxide with Example 3-11 q.s. Treated yellow iron oxide with Example 3-11q.s. Treated black iron oxide with Example 3-11 q.s. Perfume q.s.*Powder: Polymer (execution example 3-11) = 85:15 (mass %) Powder:Polymer (execution example 3-12) = 90:10 (mass %)

EXAMPLE 4-12 Powder solid foundation mass % Decamethylcyclopentasiloxane10 Dodecamethylcyclohexasiloxane 20 Trimethylsiloxysilicate 1 Poly(oxyethylene/oxypropylene) methylpolysiloxane copolymer 3 Ethanol 10Isostearic acid 0.5 Treated titania with Example 3-16 10 Treatedfineparticle zinc oxide with Example 3-16 5 Dextrin palmitate coatedtalc 5 Treated needle-shape fineparticle titania with Example 3-16 1Treated spherical anhydrous silicic acid with Example 3-16 5 Anhydroussilicic acid coated mica q.s. Sodium citrate q.s. N-Lauroyl-L-lisine 0.5DL-alpha-tocopherol acetate 0.1 D-delta-tocopherol 0.1 Sophora extract 1Treated red iron oxide with Example 3-16 q.s. Treated yellow iron oxidewith Example 3-16 q.s. Treated black iron oxide with Example 3-16 q.s.Melilot extract 2 Purified water Balance *Powder:Polymer = 80:20(mass %)

EXAMPLE 4-13 Powder solid foundation mass % Ethyl alcohol 2 Glycerin 21,3-Butylene glycol 6 Treated titania (30 μm) with Example 3-20 4Treated titania (ultrafineparticle 20 nm) with Example 3-20 2 Treatedzinc oxide with Example 3-20 2 Treated plate-shape barium sulfate withExample 3-20 5 Treated talc with Example 3-20 1 Treated kaolin withExample 3-20 2 Treated mica with Example 3-20 0.5 Treated spheric silicain Example 3-20 0.5 Salt 0.3 L-Arginine hydrochloride 0.1 Creeping thymeextract 0.1 Hamamelis 0.1 Phellodendron extract 0.1 Peppermint extractBG 0.1 Phenoxyethanol 0.5 Red iron oxide 0.5 Ocre 1 Treated iron oxideblack with Example 3-20 0.7 Magnesium aluminometasilicate 0.1Ion-exchanged water Balance *Powder:Polymer = 95:5(mass %)

EXAMPLE 4-14 Powder solid foundation mass % Ethanol 2.0 Glycerin 10.01,3-Butylene glycol 15.0 Silica coated titania 8.0 Treated syntheticphlogopite with Example 3-10 3.0 Spheric silicic anhydride 5.0 Treatedred iron oxide coated titanated mica 2.0 (color rendering pearl G) withExample 3-10 Sodium chloride 0.3 Hydroxypropyl beta-cyclodextrin 0.1Mukurossi Extract 0.1 Sweet tea extract 0.1 Lily extract 0.1 Red ironoxide 0.1 Gellan gum 0.1 Porous spheric cellulose 0.1 Lavender extract0.1 Purified water Balance *Powder:Polymer = 95:5(mass %)

EXAMPLE 4-15 POW oil-in-water emulsified milky foundation mass %  (1)Treated titania with Example 3-13 9.0  (2) Treated ultrafine particletitania(40 nm) with Example 3-13 5.0  (3) Treated iron oxide(red) withExample 3-13 0.5  (4) Treated iron oxide(yellow) with Example 3-13 1.5 (5) Treated iron oxide(black) with Example 3-13 0.2  (6)Polyoxyalkylene modified organopolysiloxane 0.5  (7)Decamethylpentacycrosiloxane 5.0  (8) Octyl p-methoxycinnamate 5.0  (9)Acrylic silicone 4.0 (10) PEG-100 hydrogenated castor oil 2.0 (11)Dynamite glycerin 6.0 (12) Xanthan Gum 0.1 (13) Carboxymethylcellulose0.3 (14) Sodium acryloyldimethyltaurate/ 1.5     hydroxy ethyl acrylatecopolymer (content: 35-40 mass %)     (SIMULGEL NSTM: Seppic)(15)Ethanol 3.0 (16) Ion-exchanged water Balance *Powder:Polymer =80:20(mass %)  (Manufacturing method) (1)-(9) were mixed and dispersed,then this was added into an aqueous phase dissolving (10)-(16) withhomomixer.

EXAMPLE 4-16 O/W type mascara mass % Microcrystalline wax 6Methylpolysiloxane emulsion q.s. Isopropanol 3 Batylalcohol 1Dipropylene glycol 5 Isostearic acid 3 Stearic acid 1Di(phytostearyl/2-octyldodecyl) N-lauroyl-L-glutamate 0.1 Sorbitanmonostearate 1 Polyoxyethylene (20EO) solbitan monostearate 1 Sucrosefatty acid ester 15 Isobutylene/sodium maleate copolymer solution 0.1Titanated mica 1 Potassium hydroxide 0.5 Sodium hydrogen carbonate 0.1DL-alpha-tocopherol acetate 0.1 Parahydroxybenzoic acid ester q.s.Sodium dehydroacetate q.s. Phenoxyethanol q.s. Treated black iron oxide(coloring material) with Example 3-13 10 Seaweed extract 0.1 Magnesiumaluminum silicate 0.1 Polyalkylacrylate emulsion 5 Polyvinyl alcohol 0.5Polyvinyl acetate emulsion 7 Purified water Balance Silicic anhydride0.5 Treated titania with Example 3-13 0.1

EXAMPLE 4-17 O/W type mascara mass % Light isoparaffin 6Dimethylpolysiloxane 1 Decamethylcyclopentasiloxane 5 Trimethylsiloxysilicate 5 Methylpolysiloxane emulsion q.s. Isopropanol 3 1,3-Butyleneglycol 6 Polyoxyethylene hydrogenated castor oil 1 Sucrose fatty acidester 0.6 Diglyceryl diisostearate 1 Sodium hydrogen carbonate 0.01DL-alpha-tocopherol acetate 0.1 Acetylated sodium hyaluronnate 0.1Parahydroxybenzoic acid ester q.s. Phenoxyethanol 0.3 Treated black ironoxide with Example 3-13 8 Bentonite 1 Dimethyldistearylammoniumhectorite 4 Polyvinyl alcohol 4 Alkylacrylate copolymer emulsion 12Polyvinyl acetate emulsion 12 Nylon fiber (1-2 mm) 6 Purified waterBalance Silicic anhydride 0.5 Treated titania with Example 3-13 1Perfume q.s.

EXAMPLE 4-18 O/W type eyeliner mass % Liquid paraffin 5Methylpolysiloxane emulsion q.s. Glycerin 3 1,3-Butylene glycol 6Polyoxyethylene (20EO) solbitan monolaurate 2 Isobutylene/sodium maleatecopolymer 1 Treated titania with Example 3-13 q.s. Plate-shape bariumsulfate q.s. Treated kaolin with Example 3-13 8 Black iron oxide coatedtitanated mica (pearl ingredient) 3 Treated black iron oxide withExample 3-13 9 DL-alpha-tocopherol acetate 0.1 Parahydroxybenzoic acidester q.s. Bentonite 1 Sodium carboxymethylcellulose 2 Alkyl acrylatecopolymer emulsion 7 Purified water Balance

EXAMPLE 4-19 Pencil-type eyeliner mass % Liquid paraffin BalanceMicrocrystalline wax 20 Macadamia nuts oil 0.1 Candelilla wax 2 Sorbitansesquiisostearate 1 Treated titania with Example 3-13 1 Treated micawith Example 3-13 5 Treated titanated mica with Example 3-13 15 Treatedsynthetic micas with Example 3-13 0.1 Treated iron blue coated titanatedmica with Example 3-13 2 Treated red iron oxide coated titanated micawith Example 3-13 2 Treated mica with Example 3-13 10DL-alpha-tocopherol acetate 0.02 D-delta-Tocopherol 0.02 Glyceryldi(p-methoxy cinnamate) mono(2-ethylhexanoate) 0.1 Treated zinc oxidewith iron blue 2 Iron blue 5 Heavy liquid isoparaffin 1 Polyalkylacrylate powder 2 Cross-linked silicone powder 5

EXAMPLE 4-20 Solid type eyeliner mass % Petrolatum 3 Hardened oil 30Japan wax 10 Stearic acid 12 Trimethylolpropane triethyloctanoate 5Treated titania with Example 3-13 2 Treated titanated mica with Example3-13 10 Treated red iron oxide with Example 3-13 2 Treated yellow ironoxide with Example 3-13 0.5 Treated iron blue with Example 3-13 5Treated black iron oxide with Example 3-13 1 Treated mica with Example3-13 Balance

EXAMPLE 4-21 Pencil-type eyebrow mass % Hardened oil 10 Macadamia nutsoil 0.1 Soybean oil 0.1 Japan wax 10 Behenic acid Balance Diisostearylmalate 1 Glyceryl tri2-ethylhexanoate 2 Sucrose fatty acid ester 5Treated titania with Example 3-13 4 Treated mica with Example 3-13 2Delta-tocopherol 0.05 Treated red iron oxide with Example 3-13 8 Treatedyellow iron oxide with Example 3-13 13 Treated black iron oxide withExample 3-13 14 Adsorption purified lanolin 5 Spheric nylon powder 3

EXAMPLE 4-22 Pencil-type eyebrow mass % Decamethylcyclopentasiloxane 10Polyoxyethylene/methylpolysiloxane copolymer 0.5Methylphenylpolysiloxane q.s. Behenyl alcohol 14 Macadamia nuts oil 0.1Carnauba wax 2 Candelilla wax 13 Sorbitan sesquiisostearate 0.5 Treatedtitania with Example 3-13 1 Treated red iron oxide coated titanated micawith Example 3-13 0.1 Treated sericite with Example 3-13 Balance Silicicanhydride 0.5 Mica 6 Delta-tocopherol 0.05 Treated red iron oxide withExample 3-13 2 Treated yellow iron oxide with Example 3-13 3 Treatedblack iron oxide with Example 3-13 8 Trimethylsiloxysilicate 8Polyethylene wax 2

EXAMPLE 4-23 Pencil-type lipliner mass % Herdened oil 20 Macadamia nutsoil 2 Japan wax 6 Behenic acid 10 Glyceryl tri2-ethylhexanoate BalanceSucrose fatty acid ester 5 Treated titania with Example 3-13 10 Treatedmica with Example 3-13 10 D-delta-tocopherol 0.04 Treated red iron oxidewith Example 3-13 13 Treated yellow iron oxide with Example 3-13 5Treated black iron oxide with Example 3-13 2 Sorbitan sesquiisostearate1

EXAMPLE 4-24 Pencil-type lipliner mass % Polyethylene wax 8 Ceresin 4Macadamia nuts oil 0.1 Liquid lanolin 0.1 Carnauba wax 1 Candelilla wax10 Phytosteryl hydroxystearate 0.1 Glyceryl triisostearate 15Diisostearyl malate 0.1 Glyceryl diisostearate BalanceTrimethylolpropane trioctanoate 5 Glyceryl tri2-ethylhexanoate 13Treated yellow iron oxide with Example 3-13 5 Treated red iron oxidewith Example 3-13 7 Treated black iron oxide with Example 3-13 0.5Treated titania with Example 3-13 0.1 Barium sulfate 1.5 Silicicanhydride 0.5 Tocopherol acetate 0.02 Delta-tocopherol 0.024-tert-butyl-4′-methoxydibenzoylmethane 0.1 Glyceryl di(p-methoxycinnamate) mono(2-ethylhexanoate) 0.1 Pigment 1 Heavy liquid isoparaffin15

EXAMPLE 4-25 Stick-type lip rouge mass % Ceresin 6Decamethylcyclopentasiloxane Balance Polyoxyethylene/methylpolysiloxanecopolymer (MW = 6000) 5 Non-aqueous dispersion 30  (Dispersion of alkylacrylate/tris(trimethylsiloxy)silylpropyl methacrylate indecamethylcycropentasiloxane) Dimethylsiloxane/diphenylsiloxane/ 20 methyl(Perfluoroalkyl)siloxane Methylphenyl polysiloxane 5Stearoxymethyl polysiloxane 2 Candelilla wax 4 Silylated silicicanhydride 1 Treated silicone coated pigments 7 (titania, iron oxide redetc.)with Example 3-13 Treated red iron oxide coated titanated mica withExample 3-13 5 Treated mica with Example 3-13 1 Dye q.s. Silicicanhydride 2 Treated titania with Example 3-13 3Poly(oxyethylene/oxypropylene)/methylpolysiloxane copolymer 2 (MW =50000) Perfume q.s.

EXAMPLE 4-26 Emulsion-type lip rouge mass % Microcrystalline wax 3Ceresin 2 Polyoxyethylene/methylpolysiloxane copolymer 0.5 Methylphenylpolysiloxane Balance Glycerin 0.5 Xylitol 0.1 Liquid lanolin 2 Squalane1 Glycerine triisostearate 1 Cholesteryl macadamiate 2 Gryceryltri(2-ethylhexanoate) 15 Glyceryl tri(hydrogenated rosinate/isostearate)10 Treated silicon resin coated titania with Example 3-13 1 Treatedcalmine coated mica titanium with Example 3-13 2 Treated titanated micawith Example 3-13 5 Dye q.s. Citric acid 0.1 Potassium hydroxide 0.05Hydroxypropyl cyclodextrin 0.3 Pantothenyl ethyl ether 0.05 Argininehydrochloride 0.01 DL-alpha-tocopherol acetate 0.05 Sodium hyaluronnate0.05 2-Ethylhexyl p-methoxycinnamate 5 Spheric cellulose powdere 2 Heavyliquid isoparaffin 20 Purified water 0.5 Perfume q.s.

EXAMPLE 4-27 Middle plate-type lip rouge mass % Liquid paraffin 11Carnauba wax 2 Glyceryl tri2-ethylhexanoate Balance Sorbitansesquioleate 1 treated titania with Example 3-13 5 Treated titanatedmica with Example 3-13 12 Treated mica with Example 3-13 17 Treated ironblue with Example 3-13 5 Treated black iron oxide in Example 3-13 1

EXAMPLE 4-28 Liquid tip-type lip rouge mass % Liquid paraffin BalanceCeresin 5 Heavy liquid isoparaffin 30 Methylphenyl polysiloxane 5 Liquidlanolin 3 Diisostearyl malate 15 Polyethylene terephtalate/polymethylmetacrylate 3 laminated film powder Treated silicone coated pigmentswith Example 3-13 3 (Bengala, iron oxide and titania, etc.) Treated rediron oxide coated titanated mica with Example 3-13 2Polyoxyethylene/methylpolysiloxane copolymer 0.5 1,3-Butylene glycol 3Hydrogenated lecithin 0.1 Calcium chloride 0.1 Sodium hyaluronnate 0.02Parabene q.s. Laponite 1.5 Purified water 1

EXAMPLE 4-29 Powder solid eye shadow mass % Liquid paraffin 0.5Petrolatum 1 Methylphenyl polysiloxane 2 Sorbitan sesquiisostearate 1Treated titania with Example 3-13 0.1 Treated mica with Example 3-13 10Treated synthetic mica with Example 3-13 2 Treated sericite with Example3-13 30 Treated talc with Example 3-13 Balance Zinc myristate 2D-delta-Tocopherol 0.02 Parahydroxybenzoic acid ester q.s. Treatedyellow iron oxide with Example 3-13 2 Treated black iron oxide withExample 3-13 20 Pigment q.s. Diisostearyl malate 3

EXAMPLE 4-30 Oily stick-type eye shadow mass % Paraffin 11 Carnauba wax1.5 Glyceryl tri2-ethylhexanoate balance Sorbitan sesquioleate 2 Treatedtitania with Example 3-13 3 Treated titanated mica with Example 3-13 15Treated mica with Example 3-13 20 Treated iron blue with Example 3-13 2Treated black iron oxide with Example 3-13 5 Perfume q.s.

EXAMPLE 4-31 Oily middle plate-type eye shadow mass % Alpha-olefineoligomer 2 Microcrystalline wax 1.5 Ceresin 6 Dimethylpolysiloxane 5Methylphenyl polysiloxane 5 Carnauba wax 2 Gryceryl tri2-ethylhexanoate20 Cetyl 2-ethylhexanoate Balance Sorbitan sesquiisostearate 1 Treatedtitania with Example 3-13 3 Treated boron nitride with Example 3-13 5Treated titanated mica with Example 3-13 10 Treated sericite withExample 3-13 8 Cross-linked silicone powder 5 DL-alpha-tocopherolacetate 0.02 D-delta-tocopherol 0.02 Treated red iron oxide with Example3-13 0.1 Treated yellow iron oxide with Example 3-13 0.2 Polyalkylacrylate powder 15 Perfume q.s. 12-Hydroxystearic acid 3

EXAMPLE 4-32 W/O type sunscreen mass % Decamethylcyclopentasiloxane 20Trimethylsiloxysilicate 1 Polyoxyethylene/methylpolysiloxane copolymer 2Dipropylene glycol 4 Squalane 5 Treated silicone coated microprticletitania (20 nm) 10 with Example 3-13 Treated talc(hydophobing material)with Example 3-13 6 Parabene q.s. Phenoxyethanol q.s. Trisodium edetate0.02 4-t-butyl-4′-methoxydibenzoylmethane 0.1 2-Ethylhexylp-methoxycinnamate 7 Glyceryl di(p-methoxycinnamate)mono(2-ethylhexanoate) 0.5 Spheric polyethylene powder 5Dimethyldistearylammonium hectorite 1 Purified water Balance Perfumeq.s.

EXAMPLE 4-33 W/O type sunscreen mass % Dimethylpolysiloxane 5Decamethylcyclopentasiloxane 20 Trimethylsiloxysilicate 3Polyoxyethylene/methylpolysiloxane copolymer 3 Dipropylene glycol 3Cetyl 2-ethylhexanoate 1 Treated silicone coating fineparticle zincoxide (60 nm) 10 with Example 3-13 Treated talc with Example 3-13 1Treated Silicone coated fineparticle titania(40 nm) 7 with Example 3-13Parabene q.s. Phenoxyethanol q.s. Trisodium edetate 0.2Dimethyldistearylammonium hectorite 1 Polymethyl methacrylate copolymerspherical powder 3 Purified water Balance Perfume q.s.

EXAMPLE 4-34 W/O type sunscreen mass % Decamethylcyclopentasiloxane 20Ethanol 5 Isostearyl alcohol 2 Dipropylene glycol 3 Isostearic acid 2Glyceryl tri2-ethylhexanoate 5 Cetyl 2-ethylhexanoate 2 Treated dextrinfatty acid ester coated 2 fineparticle titanium oxide(40 nm) withExample 3-13 Sodium chloride 2 Trisodium edetate q.s. Yubinal T-150(BASF) 1 4-t-butyl-4′-methoxydibenzoylmethane 1 Ethylhexylmethoxycinnamate 7.5 Sodium carboxymethylcellulose 0.5 Ethyl cellulose 1Spheric acrylic resin powder 5 Purified water Balance Perfume q.s.

EXAMPLE 4-35 O/W type sunscreen mass % Dimethylpolysiloxane 5Decamethylcyclopentasiloxane 25 Trimethylsiloxysilicate 5Polyoxyethylene/methylpolysiloxane copolymer 2 Dipropylene glycol 5Treated fineparticle zinc oxide (Hydrophobic treated material 15 60 nm)with Example 3-13 Parabene q.s. Phenoxyethanol q.s. Trisodium edetateq.s. 2-Ethylhexyl p-methoxycinnamate 7.5 Dimethyldistearylammoniumhectorite 0.5 Spheric polyalkyl acrylate powder 5 Purified water BalancePerfume q.s.

EXAMPLE 4-36 O/W type sunscreen mass % Dipropylene glycol 5 Stearic acid1 Palmitic acid 1 Glyceryl tri2-ethylhexanoate 3 Cetyl 2-ethylhexanoate2 Polyoxyethylene glyceryl isostearate 1 Glyceryl monostearate 1Polyoxyethylene glyceryl monostearate 1 Treated fineparticle titania (30nm) with Example 3-13 2 Sodium hexametaphosphate 0.1 Phenoxyethanol q.s.Trisodium edetate q.s. 4-t-butyl-4′-methoxydibenzoylmethane 12-Ethylhexyl p-methoxycinnamate 7 Bentonite 1 Eicosene/vinylpyrrolidonecopolymer 2 Purified water q.s. Perfume q.s.

EXAMPLE 4-37 W/O type sunscreen mass % Dimethylpolysiloxane 5Decamethylcyclopentasiloxane 25 Trimethylsiloxysilicate 5Polyoxyethylene/methylpolysiloxane copolymer 2 Dipropylene glycol 5Treated dextrin palmitate coated fineparticle zinc oxide(60 nm) 15 withExample 3-13 Dipotassium glycyrrhizinate 0.02 Glutathione 1 Thiotaurine0.05 Sophora Extract 1 Parabene q.s. Phenoxyethanol q.s. Trisodiumedetate q.s. 2-Ethylhexyl p-methoxycinnamate 7.5Dimethyldistearylammonium hectorite 0.5 Spheric polyalkyl acrylatepowder 5 Butylethylpropanediol 0.5 Purified water Balance Perfume q.s.

EXAMPLE 4-37 W/O type protector mass % Dimethylpolysiloxane 2Decamethylcyclopentasiloxane 25 Dodecamethylcyclohexasiloxane 10Polyoxyethylene/methylpolysiloxane copolymer 1.5 Trimethylsiloxysilicate1 1,3-Butylene glycol 5 Squalane 0.5 Talc 5 Dipotassium glycyrrhizinate0.1 Tocopheryl acetate 0.1 Trisodium edetate 0.054-t-butyl-4′-methoxydibenzoylmethane 1 2-Ethylhexyl p-methoxycinnamate 5Glyceryl di(p-methoxycinnamate) mono(2-ethylhexanoate) 1 Treatedsilicone coated fineparticle titania(40 nm) 4 with Example 3-13Dimethyldistearylammonium hectorite 0.5 Spheric polyethylene powder 3Phenoxyethanol q.s. Purified water Balance Perfume q.s.

1: A surface-treating agent consisting of a polymer which comprises amonomer (A) represented by the general formula (1) described below as aconstituent monomer.

wherein R¹ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R² represents an alkylene group having 4 to 22 carbonatoms, X¹ represents an —NH— group or an oxygen atom, and M¹ representsa hydrogen atom or a monovalent inorganic or organic cation. 2: Thesurface-treating agent of claim 1, wherein the polymer comprises atleast 70 mole % of monomer (A). 3: The surface-treating agent of claim1, wherein the polymer further comprises a monomer (B) represented byany one of general formulas (2) to (7):

wherein R³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁴ represents an alkylene group having 1 to 4 carbonatoms, X¹ represents an —NH— group or an oxygen atom, and M² representsa hydrogen atom or a monovalent inorganic or organic cation;

wherein R⁵ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁶ represents an alkyl group having 1 to 10 carbon atoms,a fluoroalkyl group, an aminoalkyl group, or a hydroxyalkyl group, andX³ represents an —NH— group or an oxygen atom;

wherein R⁷ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁸ represents an alkylene group having 1 to 4 carbonatoms, R⁹s may be the same or different and each represents a hydrogenatom or an alkyl group having 1 to 4 carbon atoms, X⁴ represents an —NH—group or an oxygen atom, and Y⁻ represents a monovalent organic orinorganic anion;

wherein R¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹¹ represents an alkylene group having 1 to 4 carbonatoms, R¹² represents a hydrogen atom or an alkyl group having 1 to 4carbon atoms, X⁵ represents an —NH— group or an oxygen atom, and lstands for an integer of 1 to 100;

wherein R¹³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, the constituents R¹⁴ may be the same or different and eachrepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,R¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbonatoms, X⁶ represents an —NH— group or an oxygen atom, and m stands foran integer of 1 to 100; and,

wherein R¹⁶ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹⁷ represents an alkylene group having 1 to 4 carbonatoms, X⁷ represents an —NH— group or an oxygen atom, M³ represents ahydrogen atom or a monovalent inorganic or organic cation, and n standsfor an integer of 1 to
 100. 4: The surface-treating agent of claim 3,wherein the mole ratio (A):(B) of monomer (A) to monomer (B) is from70:30 to 99.9:0.1. 5: A surface-treated powder, including a coatingcomprising the surface-treating agent of claim 1 on the powder surface.6: The surface-treated powder of claim 5, wherein the mass ratio of thepolymer to the powder is from 3:97 to 40:60. 7: A cosmetic comprisingthe surface-treating agent of claim
 1. 8: The surface-treating agent ofclaim 2, wherein the polymer further comprises a monomer (B) representedby any one of general formulas (2) to (7):

wherein R³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁴ represents an alkylene group having 1 to 4 carbonatoms, X² represents an —NH— group or an oxygen atom, and M² representsa hydrogen atom or a monovalent inorganic or organic cation;

wherein R⁵ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁶ represents an alkyl group having 1 to 10 carbon atoms,a fluoroalkyl group, an aminoalkyl group, or a hydroxyalkyl group, andX³ represents an —NH— group or an oxygen atom;

wherein R⁷ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R⁸ represents an alkylene group having 1 to 4 carbonatoms, R⁹s may be the same or different and each represents a hydrogenatom or an alkyl group having 1 to 4 carbon atoms, X⁴ represents an —NH—group or an oxygen atom, and Y⁻ represents a monovalent organic orinorganic anion;

wherein R¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹¹ represents an alkylene group having 1 to 4 carbonatoms, R¹² represents a hydrogen atom or an alkyl group having 1 to 4carbon atoms, X⁵ represents an —NH— group or an oxygen atom, and lstands for an integer of 1 to 100;

wherein R¹³ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, the two constituents R¹⁴ may be the same or different andeach represents a hydrogen atom or an alkyl group having 1 to 4 carbonatoms, R¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4carbon atoms, X⁶ represents an —NH— group or an oxygen atom, and mstands for an integer of 1 to 100; and,

wherein R¹⁶ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹⁷ represents an alkylene group having 1 to 4 carbonatoms, X⁷ represents an —NH— group or an oxygen atom, M³ represents ahydrogen atom or a monovalent inorganic or organic cation, and n standsfor an integer of 1 to
 100. 9: A surface-treated powder, including acoating comprising the surface-treating agent of claim 3 on the powdersurface. 10: A cosmetic comprising the surface-treating agent of claim2. 11: A cosmetic comprising the surface-treating agent of claim
 3. 12:A cosmetic comprising the surface-treating agent of claim
 4. 13: Acosmetic comprising the surface-treating powder of claim
 5. 14: Acosmetic comprising the surface-treating powder of claim 6.